JP4919662B2 - Uniform diffusible granular pesticide formulation - Google Patents

Uniform diffusible granular pesticide formulation Download PDF

Info

Publication number
JP4919662B2
JP4919662B2 JP2005514188A JP2005514188A JP4919662B2 JP 4919662 B2 JP4919662 B2 JP 4919662B2 JP 2005514188 A JP2005514188 A JP 2005514188A JP 2005514188 A JP2005514188 A JP 2005514188A JP 4919662 B2 JP4919662 B2 JP 4919662B2
Authority
JP
Japan
Prior art keywords
parts
granular
water
pesticide
uniform
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP2005514188A
Other languages
Japanese (ja)
Other versions
JPWO2005029956A1 (en
Inventor
清利 西山
俊雄 杉村
哲生 大川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kumiai Chemical Industry Co Ltd
Original Assignee
Kumiai Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kumiai Chemical Industry Co Ltd filed Critical Kumiai Chemical Industry Co Ltd
Priority to JP2005514188A priority Critical patent/JP4919662B2/en
Publication of JPWO2005029956A1 publication Critical patent/JPWO2005029956A1/en
Application granted granted Critical
Publication of JP4919662B2 publication Critical patent/JP4919662B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12Powders or granules
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12Powders or granules
    • A01N25/14Powders or granules wettable
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/541,3-Diazines; Hydrogenated 1,3-diazines

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

本発明は、長期間薬効を発揮させるとともに、薬害を軽減又は防止し、環境負荷を低減しうる均一拡散性粒状農薬製剤に関する。  The present invention relates to a uniformly diffusible granular agrochemical formulation that can exhibit long-term medicinal effects, reduce or prevent phytotoxicity, and reduce environmental burden.

従来より、農薬活性成分を含む粒状農薬製剤の薬害軽減や薬効持続を計るため、農薬活性成分の溶出を制御しうる製剤法が種々研究されてきた。例えば、パラフィンワックス、熱可塑性樹脂あるいは活性炭、粒状発泡体、粘土鉱物を組合せて配合し徐放化する方法などが提案されている(日本国特開昭63−35504号公報、日本国特開昭63−45201号公報及び日本国特開平2−288803号公報参照)。  Conventionally, in order to reduce the phytotoxicity and to maintain the efficacy of a granular agrochemical formulation containing an agrochemical active ingredient, various preparation methods capable of controlling the elution of the agrochemical active ingredient have been studied. For example, a method of blending paraffin wax, thermoplastic resin or activated carbon, granular foam, and clay mineral in combination and slow-releasing has been proposed (Japanese Unexamined Patent Publication No. 63-35504, Japanese Unexamined Patent Publication No. 63-45201 and Japanese Patent Laid-Open No. 2-288803).

しかし、このような従来の徐放化方法は必ずしも効果的なものではなく粒状農薬製剤の調製法が煩雑であったり、農薬組成物の放出が不充分で、農薬活性成分の大半が有効利用されずに農薬組成物中にそのまま残存してしまうなどの問題があって、必要以上の農薬活性成分が環境中に放出されることとなり、結果的に環境に対する負担が大きくなるなどの問題があった。  However, such a conventional sustained release method is not always effective, and the preparation method of the granular agricultural chemical formulation is complicated, the release of the agricultural chemical composition is insufficient, and most of the agricultural chemical active ingredients are effectively used. Without remaining in the pesticide composition as it is, and excessive pesticide active ingredients are released into the environment, resulting in an increased burden on the environment. .

また、異なる有効成分の安定化を目的に、内核を調製したのち、内核とは異なる有効成分を被覆する粒状農薬製剤の製造方法も提案されているが(日本国特開平9−315903号公報参照)、徐放化を施した粒状農薬製剤を水田畦畔からの散布などにより、水田全体に均一に拡散させる省力製剤の技術は未だ確立されていない。  In addition, for the purpose of stabilizing different active ingredients, a method for producing a granular agrochemical formulation in which an inner core is prepared and then coated with an active ingredient different from the inner core has been proposed (see Japanese Patent Laid-Open No. 9-315903). ) However, the technology of labor-saving formulation that spreads the granular agricultural chemical formulation with sustained release uniformly throughout the paddy field by spraying it from the shore of the paddy field has not been established yet.

本発明は、このような事情の下、従来の粒状農薬製剤に伴う問題点を克服し、簡便な方法で調製することができ、且つ長期にわたり農薬活性成分の薬効を発揮させるとともに、環境負荷を低減し、農薬活性成分により引き起こされる薬害を軽減又は防止しうる粒状農薬製剤を、簡便な散布法により水田全体に均一に拡散させることが可能な均一拡散性粒状農薬製剤を提供することを課題とするものである。  Under such circumstances, the present invention overcomes the problems associated with conventional granular pesticide preparations, can be prepared by a simple method, and exhibits the medicinal effects of agrochemical active ingredients over a long period of time. An object of the present invention is to provide a uniform diffusible granular pesticide formulation that can reduce and prevent the phytotoxicity caused by the pesticidal active ingredient to be uniformly diffused throughout the paddy field by a simple spraying method. To do.

本発明者らは、均一拡散性粒状農薬製剤について鋭意研究した結果、その組成を、酸性農薬活性成分にカチオン界面活性剤と塩基性物質を配合した非崩壊型粒状農薬を含有し、粒径3mm以上のものが80質量%以上である粒度分布と水面に浮遊する性質を有し、かつ30分以内に水面で崩壊させうるものとすることにより、前記の課題が解決されることを見出し、この知見に基づいて本発明をなすに至った。  As a result of diligent research on a uniform diffusible granular agricultural chemical formulation, the inventors of the present invention contain a non-disintegrating granular agricultural chemical in which an acidic agricultural chemical active ingredient is blended with a cationic surfactant and a basic substance. It has been found that the above-mentioned problems can be solved by having the particle size distribution of 80% by mass or more and the property of floating on the water surface, and being capable of collapsing on the water surface within 30 minutes. The present invention has been made based on the findings.

すなわち、本発明は、
(1)酸性農薬活性成分とカチオン界面活性剤と塩基性物質とを含有する30分以内には水中で崩壊しない非崩壊型農薬粒状物、界面活性剤及び浮遊性成分を含有し、粒径3mm以上の粒子の質量割合が80質量%以上である粒度分布と水面に投下した直後には水面に浮遊する性質を有するが、30分以内に水面で崩壊する均一拡散性粒状農薬製剤であって、
前記酸性農薬活性成分がベンスルフロンメチル及びピラゾスルフロンエチルから選ばれるスルホニルウレア系除草剤または一般式

Figure 0004919662
(式中のRは水素原子、アルキル基又はアルコキシアルキル基である)
で表されるジフルオロメタンスルホニルアニリド誘導体又はその塩であり、
前記カチオン界面活性剤が、ジ(C〜C22アルキル)ジメチルアンモニウムクロライドであって、水中でゲル化するか、あるいは膨潤性を示すものであり、かつ、
前記塩基性物質が炭酸水素ナトリウム、炭酸ナトリウム、水酸化カルシウム、炭酸カルシウム、塩基性ホワイトカーボン及び塩基性の酸性白土からなる群から選ばれる一種以上であることを特徴とする均一拡散性粒状農薬製剤、
(2)浮遊性成分が、無機中空体又はプラスチック中空体である前記(1)記載の均一拡散性粒状農薬製剤、
(3)前記(1)または(2)記載の均一拡散性粒状農薬製剤を製造するにあたり、前記非崩壊型農薬粒状物を、前記界面活性剤及び前記浮遊性成分とともに造粒処理に付し、粒径1〜20mmの球状あるいは短径1〜20mm、長径3〜40mmの横長の形状とする均一拡散性粒状農薬製剤の製造方法であって、
前記造粒処理を、前記非崩壊型農薬粒状物の粒径又は粒長よりも大きな目開き径のスクリーンより押出し造粒することにより行うことを特徴とする均一拡散性粒状農薬製剤の製造方法、
(4)前記(1)または(2)記載の均一拡散性粒状農薬製剤を製造するにあたり、前記非崩壊型農薬粒状物と、農薬活性成分とを前記界面活性剤及び前記浮遊性成分とともに造粒処理に付し、粒径1〜20mmの球状あるいは短径1〜20mm、長径3〜40mmの横長の形状とする均一拡散性粒状農薬製剤の製造方法であって、
前記造粒処理を、前記非崩壊型農薬粒状物の粒径又は粒長よりも大きな目開き径のスクリーンより押出し造粒することにより行うことを特徴とする均一拡散性粒状農薬製剤の製造方法
を提供するものである。 That is, the present invention
(1) Non-disintegrating agrochemical granular material that does not disintegrate in water within 30 minutes containing an acidic agrochemical active ingredient, a cationic surfactant and a basic substance, a surfactant and a floating component, and a particle size of 3 mm A particle size distribution in which the mass ratio of the above particles is 80% by mass or more and a property of floating on the water surface immediately after being dropped on the water surface, a uniform diffusible granular agricultural chemical formulation that collapses on the water surface within 30 minutes,
A sulfonylurea herbicide or a general formula wherein the acidic agrochemical active ingredient is selected from bensulfuron methyl and pyrazosulfuron ethyl
Figure 0004919662
(Wherein R 1 is a hydrogen atom, an alkyl group or an alkoxyalkyl group)
A difluoromethanesulfonylanilide derivative represented by
The cationic surfactant is di (C 8 -C 22 alkyl) dimethylammonium chloride, which gels in water or exhibits swelling properties; and
Uniformly diffusible granular agricultural chemical formulation, wherein the basic substance is at least one selected from the group consisting of sodium hydrogen carbonate, sodium carbonate, calcium hydroxide, calcium carbonate, basic white carbon and basic acidic clay. ,
(2) The uniform diffusible granular agricultural chemical formulation according to (1), wherein the floating component is an inorganic hollow body or a plastic hollow body,
(3) In producing the uniform diffusible granular agricultural chemical formulation according to (1) or (2), the non-disintegrating agricultural chemical granular material is subjected to granulation treatment together with the surfactant and the floating component, A method for producing a uniform diffusible granular agrochemical preparation having a spherical shape with a particle size of 1 to 20 mm or a horizontally long shape with a minor axis of 1 to 20 mm and a major axis of 3 to 40 mm,
The method for producing a uniform diffusible granular agricultural chemical formulation, wherein the granulating treatment is performed by extrusion granulation from a screen having an opening size larger than the particle size or grain length of the non-disintegrating agricultural chemical granular material,
(4) In producing the uniform diffusible granular agricultural chemical formulation according to (1) or (2), the non-disintegrating agricultural chemical granular material and the agricultural chemical active ingredient are granulated together with the surfactant and the floating ingredient. It is a method for producing a uniform diffusible granular agricultural chemical preparation that is subjected to treatment and has a spherical shape with a particle size of 1 to 20 mm or a horizontally long shape with a minor axis of 1 to 20 mm and a major axis of 3 to 40 mm,
A method for producing a uniformly diffusible granular pesticide formulation, characterized in that the granulation treatment is performed by extrusion granulation from a screen having an opening size larger than the particle size or grain length of the non-disintegrating pesticide granular material. It is to provide.

試験例2における、農薬製剤の施用処理の対象である水田圃場の説明図である。It is explanatory drawing of the paddy field which is the object of the application process of an agrochemical formulation in Test Example 2.

以下、本発明を詳細に説明する。
本発明の粒状農薬製剤に含有させる非崩壊型農薬粒状物は、30分以内には水中で崩壊せず、粒状の原型を留めるものである。
Hereinafter, the present invention will be described in detail.
The non-disintegrating agrochemical granular material contained in the granular agrochemical formulation of the present invention does not disintegrate in water within 30 minutes, and retains the granular prototype.

この非崩壊型農薬粒状物に用いられる酸性農薬活性成分については特に制限されないが、通常、除草剤、植物成長調整剤、殺菌剤、殺虫剤等であり、中でもpKa2〜7の範囲のものが好ましく、また、幾何異性体、光学異性体等も含まれる。  The acidic pesticide active ingredient used in this non-disintegrating pesticide granular material is not particularly limited, but is usually a herbicide, plant growth regulator, fungicide, insecticide, etc. Among them, those in the range of pKa 2-7 are preferable. Also included are geometrical isomers, optical isomers and the like.

除草剤としては特に制限されないが、pKa2〜7のものが好ましく、特にスルホニルウレア系化合物や、下記一般式(I)

Figure 0004919662
(式中のRは水素原子、アルキル基又はアルコキシアルキル基である)で表されるジフルオロメタンスルホニルアニリド誘導体又はその塩からなるものが特に好ましい。The herbicide is not particularly limited, but preferably has a pKa of 2 to 7, particularly sulfonylurea compounds and the following general formula (I)
Figure 0004919662
A compound comprising a difluoromethanesulfonylanilide derivative represented by the formula (wherein R 1 is a hydrogen atom, an alkyl group or an alkoxyalkyl group) or a salt thereof is particularly preferred.

スルホニルウレア系化合物の例としては、1−(4,6−ジメトキシピリミジン−2−イル)−3−[1−メチル−4−(2−メチル−2H−テトラゾール−5−イル)ピラゾール−5−イルスルホニル]尿素(アジムスルフロン)、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)、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−(4,6−ジメトキシピリミジン−2−イル)−3−(2−エトキシフェノキシスルホニル)尿素(エトキシスルフロン)、1−[2−(シクロプロピルカルボニル)アニリノスルホニル]−3−(4,6−ジメトキシピリミジン−2−イル)尿素(シクロスルファムロン)、1−(4,6−ジメトキシ−1,3,5−トリアジン−2−イル)−3−[2−(2−メトキシエトキシ)フェニルスルホニル]尿素(シノスルフロン)、メチル=3−(4−メトキシ−6−メチル−1,3,5−トリアジン−2−イルカルバモイルスルファモイル)−2−テノアート(チフェンスルフロンメチル)、2−(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)−N,N−ジメチルニコチンアミド(ニコスルフロン)、メチル=3−クロロ−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(ハロスルフロンメチル)、1−(4,6−ジメトキシピリミジン−2−イル)−3−(3−トリフルオロメチル−2−ピリジルスルホニル)尿素(フラザスルフロン)、1−(4,6−ジメトキシピリミジン−2−イル)−3−(3−エチルスルホニル−2−ピリジルスルホニル)尿素(リムスルフロン)などが挙げられる。  Examples of sulfonylurea compounds include 1- (4,6-dimethoxypyrimidin-2-yl) -3- [1-methyl-4- (2-methyl-2H-tetrazol-5-yl) pyrazol-5-yl. Sulfonyl] urea (azimylsulfuron), 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), methyl = α- (4,6-dimethoxypyrimidine-2- Ylcarbamoylsulfamoyl) -O-toluate (bensulfuronmethyl), 1- (4,6-dimethoxypyrimidine-2- L) -3- (2-ethoxyphenoxysulfonyl) urea (ethoxysulfuron), 1- [2- (cyclopropylcarbonyl) anilinosulfonyl] -3- (4,6-dimethoxypyrimidin-2-yl) urea ( Cyclosulfamlone), 1- (4,6-dimethoxy-1,3,5-triazin-2-yl) -3- [2- (2-methoxyethoxy) phenylsulfonyl] urea (sinosulfuron), methyl = 3 -(4-Methoxy-6-methyl-1,3,5-triazin-2-ylcarbamoylsulfamoyl) -2-thenoate (thifensulfuronmethyl), 2- (4,6-dimethoxypyrimidin-2-yl Rucarbamoylsulfamoyl) -N, N-dimethylnicotinamide (nicosulfuron), methyl 3-chloro-5- (4,6-dimethoxypi Limidin-2-ylcarbamoylsulfamoyl) -1-methylpyrazole-4-carboxylate (halosulfuronmethyl), 1- (4,6-dimethoxypyrimidin-2-yl) -3- (3-trifluoromethyl- 2-pyridylsulfonyl) urea (furazasulfuron), 1- (4,6-dimethoxypyrimidin-2-yl) -3- (3-ethylsulfonyl-2-pyridylsulfonyl) urea (rimsulfuron) and the like.

また、ジフルオロメタンスルホニルアニリド誘導体又はその塩の例としては、特開2000−44546号公報に記載されている化合物、例えば2−[(4,6−ジメトキシピリミジン−2−イル)ヒドロキシメチル]−N−ジフルオロメタンスルホニルアニリド、2−[(4,6−ジメトキシピリミジン−2−イル)ヒドロキシメチル]−6−メトキシメチル−N−ジフルオロメタンスルホニルアニリド、2−[(4,6−ジメトキシピリミジン−2−イル)ヒドロキシメチル]−6−エチル−N−ジフルオロメタンスルホニルアニリドなどが挙げられる。  Examples of the difluoromethanesulfonylanilide derivative or a salt thereof include compounds described in JP 2000-44546 A, such as 2-[(4,6-dimethoxypyrimidin-2-yl) hydroxymethyl] -N. -Difluoromethanesulfonylanilide, 2-[(4,6-dimethoxypyrimidin-2-yl) hydroxymethyl] -6-methoxymethyl-N-difluoromethanesulfonylanilide, 2-[(4,6-dimethoxypyrimidin-2- Yl) hydroxymethyl] -6-ethyl-N-difluoromethanesulfonylanilide and the like.

その他の除草剤の例としては、2−メチル−4−クロロフェノキシチオ酢酸−S−エチル(フェノチオール)、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)、S−(4−クロロベンジル)−N,N−ジエチルチオカルバマート(ベンチオカーブ)、S−ベンジル=1,2−ジメチルプロピル(エチル)チオカルバマート(エスプロカルブ)、S−エチルヘキサヒドロ−1H−アゼピン−1−カーボチオエート(モリネート)、S−1−メチル−1−フェニルエチル=ピペリジン−1−カルボチオアート(ジメピペレート)、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)、2−クロロ−2′,6′−ジエチル−N−(ブトキシメチル)アセトアニリド(ブタクロール)、2−クロロ−2′,6′−ジエチル−N−(2−プロポキシエチル)アセトアニリド(プレチラクロール)、(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)、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−tert−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−オキサジアゾール−2(3H)−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−トルエンスルホナート(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)、S,S′−ジメチル=2−ジフルオロメチル−4−イソブチル−6−トリフルオロメチルピリジン−3,5−ジカルボチオアート(ジチオピル)、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)、ブチル=(R)−2−[4−(4−シアノ−2−フルオロフェノキシ)フェノキシ]プロピオナート(シハロホップブチル)、3−[1−(3,5−ジクロロフェニル)−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)、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)などが挙げられる。  Examples of other herbicides include 2-methyl-4-chlorophenoxythioacetic acid-S-ethyl (phenothiol), α- (2-naphthoxy) propionanilide (naproanilide), 5- (2,4-dichlorophenoxy) ) -2-Nitrobenzoic acid methyl (biphenox), S- (4-chlorobenzyl) -N, N-diethylthiocarbamate (bench curve), S-benzyl = 1,2-dimethylpropyl (ethyl) thiocarbamate ( Esprocarb), S-ethylhexahydro-1H-azepine-1-carbothioate (molinate), S-1-methyl-1-phenylethyl = piperidine-1-carbothioate (dimethylpiperate), O-3-tert- Butylphenyl = 6-methoxy-2-pyridyl (methyl) thiocarbamate (Pyribatica B), 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) acetanilide (butachlor), 2-chloro-2', 6'-diethyl-N- (2-propoxyethyl) acetanilide (pretilachlor) (RS) -2-bromo-N- (α, α-dimethylbenzyl) -3,3-dimethylbutyramide (bromobutide), 2-benzothiazol-2-yloxy-N-methylacetanilide (mefenacet), 1- (Α, α-dimethylbenzyl) -3- (para-tolyl) urea (Dimron), 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-dimethylpropyl) Pyramino) -s-triazine (dimetamethrin), 2,4-dichlorophenyl-3'-methoxy-4'-nitrophenyl ether (clomethoxynyl), 5-tert-butyl-3- (2,4-dichloro-5-isopropoxy) Phenyl) -1,3,4-oxadiazol-2 (3H) -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 (pyrazoxyphene), (RS) -2- (2,4-dichloro-m-tolyloxy) Propionanilide (chromeprop), 2- [4- [2,4-dichloro-m-toluoyl] -1,3-di Tylpyrazol-5-yloxy] -4'-methylacetophenone (benzophenap), S, S'-dimethyl = 2-difluoromethyl-4-isobutyl-6-trifluoromethylpyridine-3,5-dicarbothioate (Dithiopyr), 2-chloro-N- (3-methoxy-2-enyl) -2 ', 6'-dimethylacetanilide (tenylchlor), butyl = (R) -2- [4- (4-cyano-2- Fluorophenoxy) phenoxy] propionate (cyhalohop butyl), 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-iso Propylidene-1,3-oxazolidine-2,4-dione (pentoxazone), 1- (diethylcarbamoyl) -3- (2,4,6-trimethylphenylsulfonyl) -1,2,4-triazole (cafentrol), methyl = 2-[(4,6-dimethoxypyrimidin-2-yl) oxy] -6-[(E) -1- (methoxyimino) ethyl] benzoate (pyriminobacmethyl) and the like.

植物成長調整剤としては、特に制限されないが、4′−クロロ−2′−(α−ヒドロキシベンジル)イソニコチンアニリド(イナベンフィド)、(2RS,3RS)−1−(4−クロロフェニル)−4,4−ジメチル−2−(1H−1,2,4−トリアゾール−1−イル)ペンタン−3−オール(パクロブトラゾール)、(E)−(S)−1−(4−クロロフェニル)−4,4−ジメチル−2−(1H−1,2,4−トリアゾール−1−イル)ペンタ−1−エン−3−オール(ウニコナゾール)、カルシウム=3−オキシド−5−オキソ−4−プロピオニルシクロヘキサ−3−エンカルボキシラート(プロヘキサジオンカルシウム塩)、マレイン酸ヒドラジドコリンなどが挙げられる。これらのうちpKa2〜7のものが特に好適に用いられる。  Although it does not restrict | limit especially as a plant growth regulator, 4'-chloro-2 '-((alpha) -hydroxy benzyl) isonicotine anilide (inavenfide), (2RS, 3RS) -1- (4-chlorophenyl) -4,4 -Dimethyl-2- (1H-1,2,4-triazol-1-yl) pentan-3-ol (paclobutrazol), (E)-(S) -1- (4-chlorophenyl) -4, 4-Dimethyl-2- (1H-1,2,4-triazol-1-yl) pent-1-en-3-ol (uniconazole), calcium = 3-oxide-5-oxo-4-propionylcyclohexa- 3-enecarboxylate (prohexadione calcium salt), maleic acid hydrazide choline and the like. Of these, those having pKa of 2 to 7 are particularly preferably used.

殺菌剤としては、特に制限されないが、O,O−ジイソプロピル−S−ベンジルチオホスフェート(IBP)、3′−イソプロポキシ−2−メチルベンズアニリド(メプロニル)、α,α,α−トリフルオロ−3′−イソプロポキシ−O−トルアニリド(フルトラニル)、3,4,5,6−テトラクロロ−N−(2,3−ジクロロフェニル)フタルアミド酸(テクロフタラム)、1−(4−クロロベンジル)−1−シクロペンチル−3−フェニル尿素(ペンシクロン)、6−(3,5−ジクロロ−4−メチルフェニル)−3(2H)−ピリダジノン(ジクロメジン)、メチル=N−(2−メトキシアセチル)−N−(2,6−キシリル)−DL−アラニナート(メタラキシル)、(E)−4−クロロ−α,α,α−トリフルオロ−N−(1−イミダゾール−1−イル−2−プロポキシエチリデン)−o−トルイジン(トリフルミゾール)、カスガマイシン、バリダマイシン、3−アリルオキシ−1,2−ベンゾイソチアゾール−1,1−ジオキシド(プロベナゾール)、ジイソプロピル−1,3−ジチオラン−2−イリデン−マロネート(イソプロチオラン)、5−メチル−1,2,4−トリアゾロ[3,4−b]ベンゾチアゾール(トリシクラゾール)、1,2,5,6−テトラヒドロピロロ[3,2,1−ij]キノリン−4−オン(ピロキロン)、5−エチル−5,8−ジヒドロ−8−オキソ[1,3]ジオキソロ[4,5−g]キノリン−7−カルボン酸(オキソリニック酸)、(Z)−2′−メチルアセトフェノン=4,6−ジメチルピリミジン−2−イルヒドラゾン−4,5,6,7−テトラクロロフタリド(フェリムゾン)、3−(3,5−ジクロロフェニル)−N−イソプロピル−2,4−ジオキソイミダゾリジン−1−カルボキサミド(イプロジオン)などが挙げられる。これらのうちpKa2〜7のものが特に好適に用いられる。  Although it does not restrict | limit especially as a disinfectant, O, O-diisopropyl-S-benzylthiophosphate (IBP), 3'-isopropoxy-2-methylbenzanilide (mepronil), (alpha), (alpha), (alpha) -trifluoro-3. '-Isopropoxy-O-toluanilide (flutranyl), 3,4,5,6-tetrachloro-N- (2,3-dichlorophenyl) phthalamic acid (teclophthalam), 1- (4-chlorobenzyl) -1-cyclopentyl -3-phenylurea (pencyclone), 6- (3,5-dichloro-4-methylphenyl) -3 (2H) -pyridazinone (dicromedin), methyl = N- (2-methoxyacetyl) -N- (2, 6-xylyl) -DL-alaninate (metalaxyl), (E) -4-chloro-α, α, α-trifluoro-N- (1-imi Sol-1-yl-2-propoxyethylidene) -o-toluidine (triflumizole), kasugamycin, validamycin, 3-allyloxy-1,2-benzisothiazole-1,1-dioxide (probenazole), diisopropyl-1, 3-dithiolane-2-ylidene-malonate (isoprothiolane), 5-methyl-1,2,4-triazolo [3,4-b] benzothiazole (tricyclazole), 1,2,5,6-tetrahydropyrrolo [3, 2,1-ij] quinolin-4-one (pyrochilone), 5-ethyl-5,8-dihydro-8-oxo [1,3] dioxolo [4,5-g] quinoline-7-carboxylic acid (oxolinic acid) ), (Z) -2′-methylacetophenone = 4,6-dimethylpyrimidin-2-ylhydrazone-4, , 6,7-tetrachloro phthalide (ferimzone), 3- (3,5-dichlorophenyl) -N- like isopropyl-2,4-dioxo-imidazolidin-1-carboxamide (iprodione). Of these, those having pKa of 2 to 7 are particularly preferably used.

殺虫剤としては特に制限されないが、O,O−ジメチル−O−(3−メチル−4−ニトロフェニル)チオホスフェート(MEP)、(2−イソプロピル−4−メチルピリミジル−6)−ジエチルチオホスフェート(ダイアジノン)、1−ナフチル−N−メチルカルバマート(NAC)、O,O−ジエチル−O−(3−オキソ−2−フェニル−2H−ピリダジン−6−イル)ホスホロチオエート(ピリダフェンチオン)、O,O−ジメチル−O−3,5,6−トリクロロ−2−ピリジルホスホロチオエート(クロルピリホスメチル)、ジメチルジカルベトキシエチルジチオホスフェート(マラソン)、O,O−ジメチル−S−(N−メチルカルバモイルメチル)ジチオホスフェート(ジメトエート)、O,O−ジプロピル−O−4−メチルチオフェニルホスフェート(プロパホス)、O,S−ジメチル−N−アセチルホスホロアミドチオエート(アセフェート)、エチルパラニトロフェニルチオノベンゼンホスホナート(EPN)、2−sec−ブチルフェニル−N−メチルカルバマート(BPMC)、2,3−ジヒドロ−2,2−ジメチル−7−ベンゾ[b]フラニル=N−ジブチルアミノチオ−N−メチルカルバマート(カルボスルファン)、エチル=N−[2,3−ジヒドロ−2,2−ジメチルベンゾフラン−7−イルオキシカルボニル(メチル)アミノチオ]−N−イソプロピル−β−アラニナート(ベンフラカルブ)、(RS)−α−シアノ−3−フェノキシベンジル=(RS)−2,2−ジクロロ−1−(4−エトキシフェニル)シクロプロパンカルボキシラート(シクロプロトリン)、2−(4−エトキシフェニル)−2−メチルプロピル=3−フェノキシベンジル=エーテル(エトフェンプロックス)、1,3−ビス(カルバモイルチオ)−2−(N,N−ジメチルアミノ)プロパン塩酸塩(カルタップ)、5−ジメチルアミノ−1,2,3−トリチアンシュウ酸塩(チオシクラム)、S,S′−2−ジメチルアミノトリメチレン=ジ(ベンゼンチオスルホナート)(ベンスルタップ)、2−tert−ブチルイミノ−3−イソプロピル−5−フェニル−1,3,5,6−テトラヒドロ−2H−1,3,5−チアジアジン−4−オン(ブプロフェジン)などが挙げられる。これらのうちpKa2〜7のものが特に好適に用いられる。  The insecticide is not particularly limited, but O, O-dimethyl-O- (3-methyl-4-nitrophenyl) thiophosphate (MEP), (2-isopropyl-4-methylpyrimidyl-6) -diethylthiophosphate (diazinone) ), 1-naphthyl-N-methylcarbamate (NAC), O, O-diethyl-O- (3-oxo-2-phenyl-2H-pyridazin-6-yl) phosphorothioate (pyridafenthione), O, O-dimethyl -O-3,5,6-trichloro-2-pyridyl phosphorothioate (chlorpyrifosmethyl), dimethyldicarbethoxyethyl dithiophosphate (marathon), O, O-dimethyl-S- (N-methylcarbamoylmethyl) dithiophosphate (dimethoate) ), O, O-dipropyl-O-4-methylthio Phenyl phosphate (propaphos), O, S-dimethyl-N-acetylphosphoramidothioate (acephate), ethyl paranitrophenylthionobenzenephosphonate (EPN), 2-sec-butylphenyl-N-methylcarbamate ( BPMC), 2,3-dihydro-2,2-dimethyl-7-benzo [b] furanyl = N-dibutylaminothio-N-methylcarbamate (carbosulfan), ethyl = N- [2,3-dihydro -2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio] -N-isopropyl-β-alaninate (benfuracarb), (RS) -α-cyano-3-phenoxybenzyl = (RS) -2,2 -Dichloro-1- (4-ethoxyphenyl) cyclopropanecarboxylate (cyclo Rotrin), 2- (4-ethoxyphenyl) -2-methylpropyl = 3-phenoxybenzyl ether (ethofenprox), 1,3-bis (carbamoylthio) -2- (N, N-dimethylamino) propane Hydrochloride (cartap), 5-dimethylamino-1,2,3-trithian oxalate (thiocyclam), S, S'-2-dimethylaminotrimethylene di (benzenethiosulfonate) (bensulfap), 2 -Tert-butylimino-3-isopropyl-5-phenyl-1,3,5,6-tetrahydro-2H-1,3,5-thiadiazin-4-one (buprofezin) and the like. Of these, those having pKa of 2 to 7 are particularly preferably used.

上記所定pKaの酸性農薬活性成分を用いる場合、該成分のpKaは、例えば丸善(株)昭和33年1月20日発行、実験化学講座5(熱的測定および平衡)p469〜p474に記載されている方法等で測定される。  When the acidic pesticide active ingredient having the predetermined pKa is used, the pKa of the ingredient is described in, for example, Maruzen Co., Ltd. issued on January 20, 1958, Experimental Chemistry Course 5 (Thermal Measurement and Equilibrium) p469-p474. It is measured by the method.

本発明に用いられるカチオン界面活性剤については、特に制限されないが、好ましくはアミン塩系、ピリジニウム塩系、第四級アンモニウム塩系などのものが挙げられる。  The cationic surfactant used in the present invention is not particularly limited, but preferably includes amine salt type, pyridinium salt type, quaternary ammonium salt type and the like.

アミン塩系カチオン界面活性剤の例としては、ラウリルアミン塩酸塩、ステアリルアミン塩酸塩、オレイルアミン酢酸塩、ステアリルアミン酢酸塩、ステアリルアミノプロピルアミン酢酸塩などが挙げられる。  Examples of amine salt cationic surfactants include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate and the like.

ピリジニウム塩系カチオン界面活性剤の例としては、ラウリルピリジニウムクロライド、ミリスチルピリジニウムクロライド、セチルピリジニウムクロライドなどが挙げられる。  Examples of pyridinium salt cationic surfactants include lauryl pyridinium chloride, myristyl pyridinium chloride, cetyl pyridinium chloride and the like.

第四級アンモニウム塩系カチオン界面活性剤の例としては、アルキルジメチルベンジルアンモニウムクロライド、ラウリルトリメチルアンモニウムクロライド、セチルトリメチルアンモニウムクロライド、ステアリルトリメチルアンモニウムクロライド、ジラウリルジメチルアンモニウムクロライド、ジオレイルジメチルアンモニウムクロライド、ジココイルジメチルアンモニウムクロライド、ジステアリルジメチルアンモニウムクロライド、ラウリルジヒドロキシエチルメチルアンモニウムクロライド、オレイルビスポリオキシエチレンメチルアンモニウムクロライド、ステアリルヒドロキシエチルジメチルアンモニウムクロライド、ラウリルジメチルベンジルアンモニウムクロライド、ラウロイルアミノプロピルジメチルエチルアンモニウムエトサルフェート、ラウロイルアミノプロピルジメチルヒドロキシエチルアンモニウムパークロレートなどが挙げられる。  Examples of quaternary ammonium salt cationic surfactants include alkyldimethylbenzylammonium chloride, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, dilauryldimethylammonium chloride, dioleyldimethylammonium chloride, dicocoyl. Dimethylammonium chloride, distearyldimethylammonium chloride, lauryldihydroxyethylmethylammonium chloride, oleylbispolyoxyethylenemethylammonium chloride, stearylhydroxyethyldimethylammonium chloride, lauryldimethylbenzylammonium chloride, lauroylaminopropyldimethylethylammonium Arm ethosulfate, etc. lauroyl aminopropyl dimethyl hydroxyethyl ammonium perchlorate and the like.

カチオン界面活性剤として特に好適なものは、水中でゲル化するか、あるいは膨潤性を示すもの、例えばジアルキルジメチルアンモニウムクロライドであって、そのアルキル部分がC8〜C22であるもの、中でもジラウリルジメチルアンモニウムクロライド、ジオレイルジメチルアンモニウムクロライド、ジココイルジメチルアンモニウムクロライド、ジステアリルジメチルアンモニウムクロライドなどである。これらの界面活性剤は単独で用いてもよいし、また、2種以上を組み合わせて用いてもよい。  Particularly suitable as the cationic surfactant is one that gels or swells in water, such as dialkyldimethylammonium chloride, the alkyl part of which is C8 to C22, and in particular dilauryldimethylammonium. Chloride, dioleyl dimethyl ammonium chloride, dicocoyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride and the like. These surfactants may be used alone or in combination of two or more.

本発明に用いられる塩基性物質は、特に制限されないが、好ましくは1質量%水溶液あるいは1質量%水懸濁液としたときに、pHが7.5以上、中でも9〜12であるものが好ましい。このようなものとしては、アルカリ金属やアルカリ土類金属の水酸化物、アルカリ金属塩やアルカリ土類金属塩、それを含む化合物や鉱物類などが挙げられる。さらに具体的には水酸化ナトリウム、水酸化カリウム、炭酸水素ナトリウム、炭酸ナトリウム、水酸化カルシウム、炭酸カルシウム、酸化カルシウム、塩基性ホワイトカーボン、塩基性の酸性白土などが挙げられ、特に、炭酸水素ナトリウム、炭酸ナトリウム、水酸化カルシウム、炭酸カルシウム、塩基性ホワイトカーボン及び塩基性の酸性白土が好ましい。これらの塩基性物質は単独で用いてもよいし、また、2種以上を組み合わせて用いてもよい。  The basic substance used in the present invention is not particularly limited, but preferably has a pH of 7.5 or more, particularly 9 to 12 when a 1% by mass aqueous solution or 1% by mass aqueous suspension is used. . Examples of such materials include alkali metal and alkaline earth metal hydroxides, alkali metal salts and alkaline earth metal salts, and compounds and minerals containing the same. More specifically, sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, calcium hydroxide, calcium carbonate, calcium oxide, basic white carbon, basic acidic clay, etc., in particular, sodium hydrogen carbonate Sodium carbonate, calcium hydroxide, calcium carbonate, basic white carbon and basic acidic clay are preferred. These basic substances may be used alone or in combination of two or more.

本発明に用いられる界面活性剤は特に制限されず、例えば、ポリオキシアルキレングリコール高級脂肪酸エステル、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルキルアリールエーテル、ポリオキシアルキレンアルキルアリールフェニルエーテル、ソルビタンモノアルキレート、アセチレングリコール、ポリオキシエチレンアセチレングリコール等のノニオン界面活性剤、アルキルアリールスルホン酸塩、ジアルキルスルホン酸塩、アルキル硫酸エステル塩、アルキルリン酸エステル塩、アルキルアリールリン酸塩、アルキルアリールリン酸エステル塩、ポリオキシアルキレンアルキルエーテル硫酸エステル塩、ナフタレンスルホン酸塩及びその縮合物、アルキルナフタレンスルホン酸塩及びその縮合物、リグニンスルホン酸塩、アクリル酸−イタコン酸共重合体、メタクリル酸−イタコン酸共重合体、マレイン酸−スチレン共重合体、マレイン酸−イソブチレン共重合体、及びこれらのアルカリ金属塩等のポリカルボン酸型高分子界面活性剤、ポリオキシアルキレンアリールフェニルエーテル硫酸エステル塩等のアニオン界面活性剤などが挙げられる。これらは単独で用いてもよいし、また、2種以上を組み合わせて用いてもよい。  The surfactant used in the present invention is not particularly limited. For example, polyoxyalkylene glycol higher fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl aryl ether, polyoxyalkylene alkyl aryl phenyl ether, sorbitan monoalkylate, Nonionic surfactants such as acetylene glycol and polyoxyethylene acetylene glycol, alkylaryl sulfonates, dialkyl sulfonates, alkyl sulfate esters, alkyl phosphate esters, alkylaryl phosphates, alkylaryl phosphate esters, Polyoxyalkylene alkyl ether sulfate, naphthalene sulfonate and its condensate, alkyl naphthalene sulfonate and its condensate, lignin sulfate Polycarboxylic acid types such as phosphate, acrylic acid-itaconic acid copolymer, methacrylic acid-itaconic acid copolymer, maleic acid-styrene copolymer, maleic acid-isobutylene copolymer, and alkali metal salts thereof Examples thereof include a polymeric surfactant and an anionic surfactant such as a polyoxyalkylene aryl phenyl ether sulfate ester salt. These may be used alone or in combination of two or more.

本発明に用いられる浮遊性物質は水面に投下したとき、それ自体が水面に浮遊するものであればよく、特に限定されないが、無機物としては、例えばガラス質中空体、発泡パーライト、発泡フライアッシュ、バーミキュライト、焼成バーミキュライト、シラスバルーン、マイクロバルーン、セノスフェア等の無機中空体等が、また、有機物としては、プラスチック中空体、ロウ類、固形パラフィン類、泡を含んだ澱粉、コルク、木片、コーンコブ等の植物片、ポリブテン等の比重の軽い有機溶剤等がそれぞれ挙げられる。特に、ガラス質中空体及びシラス加熱発泡体等の無機中空体または塩化ビニリデン・アクリロニトリル共重合物プラスチックバルーン及びアクリロニトリル系プラスチックバルーン等のプラスチック中空体が好ましい。これらは単独で用いてもよいし、また、2種以上を組み合わせて用いてもよい。  The floating substance used in the present invention is not particularly limited as long as it floats on the water surface when dropped on the water surface, and as an inorganic substance, for example, a glassy hollow body, foamed perlite, foamed fly ash, Inorganic hollow bodies such as vermiculite, calcined vermiculite, shirasu balloon, microballoon, cenosphere, etc., and organic substances such as plastic hollow bodies, waxes, solid paraffins, foamed starch, cork, wood chips, corn cob, etc. Examples thereof include light organic solvents such as plant fragments and polybutene. In particular, inorganic hollow bodies such as glassy hollow bodies and shirasu heating foams, or plastic hollow bodies such as vinylidene chloride / acrylonitrile copolymer plastic balloons and acrylonitrile plastic balloons are preferred. These may be used alone or in combination of two or more.

本発明の均一拡散性粒状農薬製剤には、必要に応じ農薬製剤に通常用いられる添加成分を含有させることができる。この添加成分としては、増量剤、補助成分などが用いられる。  The uniform diffusible granular agricultural chemical formulation of the present invention can contain additive components usually used in agricultural chemical formulations as necessary. As this additive component, a bulking agent, an auxiliary component and the like are used.

増量剤としては、鉱物質担体などの固体担体や、水溶性塩等が用いられ、具体的にはクレー類、炭酸カルシウム、ベントナイト、タルク、珪藻土、酸性白土、けい砂、粒状炭酸カルシウム、粒状珪藻土、ステアリン酸カルシウム、ホワイトカーボン、塩化カリウム、無水硫酸ナトリウム、硫酸カリウム、尿素、硫酸アンモニウム、安息香酸ナトリウム等が挙げられる。これらは単独で用いてもよいし、また、2種以上を組み合わせて用いてもよい。  As the extender, solid carriers such as mineral carriers, water-soluble salts, etc. are used. Specifically, clays, calcium carbonate, bentonite, talc, diatomaceous earth, acid clay, silica sand, granular calcium carbonate, granular diatomaceous earth. , Calcium stearate, white carbon, potassium chloride, anhydrous sodium sulfate, potassium sulfate, urea, ammonium sulfate, sodium benzoate and the like. These may be used alone or in combination of two or more.

補助成分としては、例えば粒状組成物を調製する際の結合剤、具体的にはカルボキシメチルセルロースナトリウム塩、デキストリン、水溶性デンプン、キサンタンガム、グアーガム、蔗糖、ポリビニルピロリドン、ポリビニルアルコール、ポリアクリル酸ナトリウム、平均分子量6000〜20000のポリエチレングリコール、平均分子量10万〜500万のポリエチレンオキサイドなどが挙げられる。また、酸性農薬活性成分及びカチオン界面活性剤を溶解させて担体に吸着させる際に用いる有機溶剤、具体的には、アルキルナフタレン、ジメチルホルムアミド、ジメチルスルホキシド、N−メチル−2−ピロリドン、N−オクチルピロリドン、多価アルコール、シリコーンオイルなどが挙げられる。その他必要に応じ、安定剤等を用いてもよい。これらは単独で用いてもよいし、また、2種以上を組み合わせて用いてもよい。  As an auxiliary component, for example, a binder in preparing a granular composition, specifically carboxymethylcellulose sodium salt, dextrin, water-soluble starch, xanthan gum, guar gum, sucrose, polyvinylpyrrolidone, polyvinyl alcohol, sodium polyacrylate, average Examples thereof include polyethylene glycol having a molecular weight of 6000 to 20000, polyethylene oxide having an average molecular weight of 100,000 to 5,000,000, and the like. Further, an organic solvent used for dissolving an acidic pesticidal active ingredient and a cationic surfactant and adsorbing them on a carrier, specifically, alkylnaphthalene, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-octyl Examples include pyrrolidone, polyhydric alcohol, and silicone oil. In addition, you may use a stabilizer etc. as needed. These may be used alone or in combination of two or more.

本発明の均一拡散性粒状農薬製剤において、非崩壊型農薬粒状物の組成割合については、通常、酸性農薬活性成分0.1〜40質量%、カチオン界面活性剤1〜40質量%、塩基性物質0.1〜95質量%の範囲で選ばれ、好ましくは非崩壊型農薬粒状物の1質量%水懸濁液のpHが通常5以上、好ましくは7以上、より好ましくは7.5〜11.5となるように調整される。  In the uniform diffusible granular agricultural chemical formulation of the present invention, the composition ratio of the non-disintegrating agricultural chemical granular material is usually 0.1 to 40% by mass of an acidic agricultural chemical active ingredient, 1 to 40% by mass of a cationic surfactant, and a basic substance. It is selected in the range of 0.1 to 95% by mass, and preferably the pH of the 1% by mass aqueous suspension of the non-disintegrating agrochemical granular material is usually 5 or more, preferably 7 or more, more preferably 7.5 to 11. It is adjusted to be 5.

また、本発明の均一拡散性粒状農薬製剤の組成割合については、通常、非崩壊型農薬粒状物1〜70質量%、農薬活性成分0〜50質量%、界面活性剤0.1〜30質量%、浮遊性成分0.1〜50質量%、増量剤0〜95質量%、好ましくは5〜70質量%、補助成分0〜50質量%、好ましくは0.1〜30質量%の範囲で選ばれ、さらに好ましくは1粒の比重が1未満で、水面に浮遊させるに足るような範囲で選ばれる。  Moreover, about the composition ratio of the uniform diffusible granular agrochemical formulation of this invention, normally 1-70 mass% of non-disintegrating agrochemical granular materials, agrochemical active ingredient 0-50 mass%, surfactant 0.1-30 mass% , Floating component 0.1-50% by mass, extender 0-95% by mass, preferably 5-70% by mass, auxiliary component 0-50% by mass, preferably 0.1-30% by mass. More preferably, the specific gravity of one grain is less than 1, and it is selected in a range sufficient to float on the water surface.

本発明の均一拡散性粒状農薬製剤は、圃場での処理後、30分以内に崩壊し、崩壊途中で徐々に、それ自体に含有される非崩壊型農薬粒状物を、圃場に均一に沈降させ、該農薬粒状物に含有される農薬活性成分の溶出を徐放化させた、省力化型の放出制御農薬製剤であるが、徐放化させたくない農薬活性成分を非崩壊型農薬粒状物とは別に均一拡散性粒状農薬製剤に含有させることで、各農薬活性成分に合った溶出性を設計することも可能である。  The uniform diffusible granular pesticide preparation of the present invention disintegrates within 30 minutes after the treatment in the field, and gradually settles the non-disintegrating pesticide granular material contained in itself uniformly in the field during the disintegration. , Which is a labor-saving release-controlled pesticide formulation in which elution of the pesticide active ingredient contained in the pesticide granule is sustainedly released, but the pesticide active ingredient that is not desired to be sustainedly released is defined as a non-disintegrating pesticide granule It is also possible to design a dissolution property suitable for each pesticidal active ingredient by including it in a uniform diffusible granular pesticide formulation.

また、本発明は、この均一拡散性粒状農薬製剤と、カチオン界面活性剤も塩基性物質もともに有しない均一拡散性粒状農薬製剤とを1:9〜9:1の質量比で混合してなる混合農薬製剤をも包含する。  Moreover, this invention mixes this uniform diffusible granular agricultural chemical formulation and the uniform diffusible granular agricultural chemical formulation which has neither a cationic surfactant nor a basic substance by mass ratio of 1: 9-9: 1. Includes mixed agrochemical formulations.

本発明の均一拡散性粒状農薬製剤において、それ自体のサイズは、球状では通常、粒径1〜20mm、好ましくは3〜10mm、横長の形状では通常、短径1〜20mm、好ましくは3〜10mm、長径3〜40mm、好ましくは5〜30mmとするのがよく、この農薬製剤中に包含される非崩壊型農薬粒状物のサイズは、球状では通常、粒径0.01〜5mm、好ましくは0.1〜3mm、横長の形状では通常、短径0.1〜10mm、好ましくは0.5〜7mm、長径0.3〜30mm、好ましくは1.5〜20mmとするのがよい。  In the uniform diffusible granular agricultural chemical preparation of the present invention, the size itself is usually 1 to 20 mm, preferably 3 to 10 mm, in a spherical shape, and usually 1 to 20 mm, preferably 3 to 10 mm, in a horizontally long shape. The major axis is 3 to 40 mm, preferably 5 to 30 mm, and the size of the non-disintegrating pesticide granular material included in the agricultural chemical formulation is usually 0.01 to 5 mm, preferably 0, in the spherical shape. In the case of a horizontally long shape, the minor axis is usually 0.1 to 10 mm, preferably 0.5 to 7 mm, and the major axis is 0.3 to 30 mm, preferably 1.5 to 20 mm.

本発明の均一拡散性粒状農薬製剤及び該製剤中に含有される非崩壊型農薬粒状物を調製する方法については特に制限されず、例えば、従来より知られた、転動造粒法、押出し造粒法、コーティング造粒法等が用いられる。  The method for preparing the uniform diffusible granular agricultural chemical formulation of the present invention and the non-disintegrating agricultural chemical granular material contained in the pharmaceutical formulation is not particularly limited. For example, conventionally known rolling granulation method, extrusion molding A granulation method, a coating granulation method, or the like is used.

本発明の均一拡散性粒状農薬製剤の製法として、好ましくは、酸性農薬活性成分とカチオン界面活性剤と塩基性物質とを含有する30分以内には水中で崩壊しない非崩壊型農薬粒状物を界面活性剤及び浮遊性成分とともに造粒処理に付し、粒径1〜20mmの球状あるいは短径1〜20mm、長径3〜40mmの横長の形状とする方法が挙げられる。
(非崩壊型農薬粒状物の製造)
As a method for producing the uniform diffusible granular agricultural chemical formulation of the present invention, preferably, the non-disintegrating agricultural chemical granular material that does not disintegrate in water within 30 minutes containing an acidic agricultural chemical active ingredient, a cationic surfactant and a basic substance is interfaced. Examples include a method of subjecting to a granulation treatment together with an activator and a floating component to form a spherical shape having a particle size of 1 to 20 mm, or a horizontally long shape having a minor axis of 1 to 20 mm and a major axis of 3 to 40 mm.
(Manufacture of non-disintegrating pesticide particulates)

転動造粒法は、酸性農薬活性成分、カチオン界面活性剤及び塩基性物質を結合剤や増量剤等の補助成分とともに転動造粒機に入れ、粉粒状原料を調製する工程、この粉粒状原料に適量の水或いは結合剤を溶解した水溶液を徐々に加えて目標の粒度や粒長をもつ粒状組成物を調製する工程及びこの粒状組成物を、必要に応じその表面にフィルム形成物質をコーティングし、乾燥したのち、篩い分ける工程からなる。  The tumbling granulation method is a process of preparing a granular raw material by adding an acidic pesticide active ingredient, a cationic surfactant and a basic substance together with auxiliary components such as a binder and a bulking agent to prepare a granular raw material. A step of preparing a granular composition having a target particle size and particle length by gradually adding an appropriate amount of water or an aqueous solution in which a binder is dissolved in the raw material, and coating the film forming material on the surface of this granular composition as necessary And drying, and then sieving.

押出し造粒法は、酸性農薬活性成分、カチオン界面活性剤及び塩基性物質を結合剤や増量剤等の補助成分とともにエアミル粉砕或いはメカノケミカル粉砕し、粉末状原料を調製する工程、この粉末状原料に適量の水を加えた混合物を、二軸型ニーダーのようなニーダー、押出し造粒機等で捏和した後、目標の粒度や粒長をもつように目開き径を設定したスクリーンより押出し造粒して粒状組成物を調製する工程及びこの粒状組成物を、必要に応じその表面にフィルム形成物質をコーティングし、乾燥したのち、篩い分ける工程からなる。  The extrusion granulation method is a process of preparing a powdery raw material by air mill grinding or mechanochemical grinding of acidic agrochemical active ingredients, cationic surfactants and basic substances together with auxiliary components such as binders and extenders, and this powdery raw material. After kneading the mixture with an appropriate amount of water in a kneader such as a twin-screw kneader or an extrusion granulator, etc., the mixture is extruded from a screen that has an opening size set to have the target particle size and grain length. It comprises a step of preparing a granular composition by granulation, and a step of coating the granular composition with a film-forming substance on the surface, if necessary, and then sieving.

コーティング造粒法は、酸性農薬活性成分、塩基性物質、及び必要に応じ用いられるカチオン界面活性剤、増量剤等の補助成分をエアミル粉砕或いはメカノケミカル粉砕し、粉末状原料を調製する工程、目標の粒度や粒長をもつ吸油性粒状物を円錐スクリュー型混合機に入れ、溶剤で希釈したカチオン界面活性剤、必要に応じ用いられる結合剤等の補助成分を同時にスプレーしながら混合して得た吸油性粒状物に、前工程で得た粉末状原料をコーティングし、粒状組成物を調製する工程及びこの粒状組成物を、必要に応じ乾燥したのち、篩い分ける工程からなる。
(粒状農薬製剤の製造)
The coating granulation method is a process for preparing a powdery raw material by subjecting acidic agrochemical active ingredients, basic substances, and auxiliary components such as cationic surfactants and extenders used as needed to air mill grinding or mechanochemical grinding, The oil-absorbing granular material having a particle size and particle length of 1 μm was placed in a conical screw type mixer and mixed while simultaneously spraying auxiliary components such as a cationic surfactant diluted with a solvent and a binder used as needed. The powdery raw material obtained in the previous step is coated on the oil-absorbing granular material to prepare a granular composition, and the granular composition is dried if necessary and then sieved.
(Manufacture of granular agricultural chemicals)

押出し造粒法は、先の製法により得た非崩壊型農薬粒状物、界面活性剤及び浮遊性成分を、必要に応じ用いられる増量剤、結合剤や安定剤等の補助成分ならびに農薬活性成分とともに二軸型ニーダーのようなニーダー、押出し造粒機等で適量の水を加え捏和し、得られた混合物を非崩壊型農薬粒状物の粒度や粒長よりも大きな目開き径のスクリーンから押出し造粒して粒状組成物を調製する工程及びこの粒状組成物を、必要に応じその表面にフィルム形成物質をコーティングし、乾燥したのち、篩い分ける工程からなる。  The extrusion granulation method uses non-disintegrating pesticide granules obtained by the previous production method, surfactants and floating components, together with auxiliary components such as extenders, binders and stabilizers and pesticide active components used as necessary. Add a suitable amount of water with a kneader such as a twin-screw kneader or an extrusion granulator, knead, and extrude the resulting mixture from a screen with an opening size larger than the particle size and particle length of the non-disintegrating pesticide granule. It comprises a step of granulating to prepare a granular composition, and a step of coating the granular composition with a film-forming substance on the surface, if necessary, drying and then sieving.

転動造粒法は、先の製法により得た非崩壊型農薬粒状物、界面活性剤及び浮遊性成分を、必要に応じ用いられる増量剤、結合剤や安定剤等の補助成分ならびに農薬活性成分とともに転動造粒機に入れ、粉粒状原料を調製する工程、この粉粒状原料に適量の水或いは結合剤を溶解した水溶液を徐々に加えて目標の粒度や粒長をもつ粒状組成物を調製する工程及びこの粒状組成物を、必要に応じその表面にフィルム形成物質をコーティングし、乾燥したのち、篩い分ける工程からなる。  The rolling granulation method is based on the non-disintegrating pesticide granules obtained by the previous production method, surfactants and floating components, auxiliary components such as extenders, binders and stabilizers, and pesticide active components. In addition, it is put into a tumbling granulator to prepare a granular raw material, and an aqueous solution in which an appropriate amount of water or a binder is dissolved is gradually added to the granular raw material to prepare a granular composition having a target particle size and particle length. And a step of coating the granular composition with a film-forming substance on the surface thereof, if necessary, and drying and then sieving.

これらの製法において、乾燥処理は、流動層乾燥装置、真空乾燥装置等の適当な乾燥装置で行うのがよい。  In these production methods, the drying treatment is preferably performed with an appropriate drying device such as a fluidized bed drying device or a vacuum drying device.

本発明の均一拡散性粒状農薬製剤においては、酸性農薬活性成分としてpKa2〜7のもの、中でも除草剤、例えばスルホニルウレア系化合物からなる除草剤、特に前記一般式(I)で表されるジフルオロメタンスルホニルアニリド誘導体又はその塩を、また、カチオン界面活性剤として水中でゲル化するか、あるいは膨潤性を示すものを用いるのが好ましい。  In the uniform diffusible granular agricultural chemical formulation of the present invention, the active ingredients of pKa 2-7 are acidic herbicides, especially herbicides such as herbicides comprising sulfonylurea compounds, especially difluoromethanesulfonyl represented by the above general formula (I) It is preferable to use an anilide derivative or a salt thereof as a cationic surfactant that gels in water or exhibits swelling properties.

以下、本発明を実施例および試験例にて詳細に説明するが、本発明はこれらの例により何ら制限されるものではない。なお、各例において部は質量部を表わす。  EXAMPLES Hereinafter, although an Example and a test example demonstrate this invention in detail, this invention is not restrict | limited at all by these examples. In addition, in each example, a part represents a mass part.

実施例で用いた農薬活性成分はいずれもpKa2〜7のものであり、塩基性物質はいずれも1質量%水溶液、あるいは1質量%水懸濁液でpHが7.5以上のものであり、非崩壊型農薬粒状物はいずれも1質量%水懸濁液でpHが5以上のものであった。  The pesticide active ingredients used in the examples are all having a pKa of 2 to 7, and the basic substances are all 1% by mass aqueous solution or 1% by mass aqueous suspension with a pH of 7.5 or more. All of the non-disintegrating pesticide particulates were 1% by mass aqueous suspensions having a pH of 5 or more.

また、実施例1、7、9〜10で用いたカチオン界面活性剤はいずれも水中でゲル化するものであった。  Moreover, all the cationic surfactants used in Examples 1, 7, and 9 to 10 gelled in water.

さらに、各実施例で得られた均一拡散性粒状農薬製剤は、水面に投下した直後には水面に浮遊したが、30分以内に崩壊し、非崩壊型農薬粒状物が沈降した。  Furthermore, the uniform diffusible granular agricultural chemical formulation obtained in each Example floated on the water surface immediately after dropping on the water surface, but disintegrated within 30 minutes, and the non-disintegrating agricultural chemical granular material settled.

ベンスルフロンメチル(pKa5.03)6.25部、ジステアリルジメチルアンモニウムクロライド6.25部、ジラウリルジメチルアンモニウムクロライド6.25部、炭酸カルシウム68.75部、ポリビニルアルコール6.25部、α化でんぷん6.25部を均一に混合した混合物を、衝撃式粉砕機で粉砕した。得られた粉末を高速撹拌機中で適量の水を加えて混練したのち、ドーム型造粒機を用い目開き径0.5mmのスクリーンより押出し造粒し、造粒物を60℃で静置乾燥して、ベンスルフロンメチルを6.25質量%含有する、直径0.4〜0.6mm、長さ1〜6mmの農薬粒状物を得た。得られた農薬粒状物を水中に投下し、30分後に粒の崩壊状態を観察したところ、崩壊した粒は認められず、非崩壊型と判定された。  Bensulfuron methyl (pKa 5.03) 6.25 parts, distearyldimethylammonium chloride 6.25 parts, dilauryldimethylammonium chloride 6.25 parts, calcium carbonate 68.75 parts, polyvinyl alcohol 6.25 parts, pregelatinized starch The mixture in which 6.25 parts were uniformly mixed was pulverized with an impact pulverizer. The obtained powder was kneaded with an appropriate amount of water in a high-speed stirrer, and then extruded and granulated from a screen having an aperture diameter of 0.5 mm using a dome type granulator, and the granulated product was allowed to stand at 60 ° C. It dried and obtained the agrochemical granule of diameter 0.4-0.6mm and length 1-6mm containing 6.25 mass% of bensulfuron methyl. The obtained agrochemical granular material was dropped into water, and the collapsed state of the particles was observed after 30 minutes. As a result, no collapsed particles were observed, and the particles were determined to be non-disintegrating.

次に、非崩壊型農薬粒状物32部、ポリオキシエチレンアセチレングリコール3部、酵素変性デキストリン2部、プラスチック中空体として塩化ビニリデン・アクリロニトリル共重合物プラスチックバルーン[マツモトマイクロスフェアーF−30E(商品名)、松本油脂製薬株式会社製]14部、無水硫酸ナトリウム20部、尿素40.9部に適量の水を加えた混合物を二軸型ニーダーで混練したのち、押出し造粒機を用い目開き径5mmのスクリーンより押出し造粒し、目標の大きさになるように整粒したのち、品温60℃で流動層乾燥機により乾燥し、篩い分けることにより、直径3〜7mm、長さ3〜20mmのベンスルフロンメチル2質量%を含有する粒状物を均一拡散性粒状農薬製剤として得た。得られた均一拡散性粒状農薬製剤を水中に投下し、観察した結果、30分以内で該製剤の粒子が崩壊し、非崩壊型農薬粒状物は沈降した。  Next, 32 parts of non-disintegrating pesticide particulates, 3 parts of polyoxyethylene acetylene glycol, 2 parts of enzyme-modified dextrin, vinylidene chloride / acrylonitrile copolymer plastic balloon [Matsumoto Microsphere F-30E (trade name) as a plastic hollow body ), Matsumoto Yushi Seiyaku Co., Ltd.] 14 parts, 20 parts of anhydrous sodium sulfate, 40.9 parts of urea and a suitable amount of water were kneaded in a twin-screw kneader, and then the opening diameter was measured using an extrusion granulator. After extruding and granulating from a 5 mm screen, adjusting the size to the target size, drying with a fluidized bed dryer at a product temperature of 60 ° C., and sieving, a diameter of 3 to 7 mm and a length of 3 to 20 mm A granular material containing 2% by mass of bensulfuron methyl was obtained as a uniformly diffusible granular agricultural chemical preparation. As a result of dropping and observing the obtained uniformly diffusible granular agricultural chemical formulation in water, the particles of the pharmaceutical formulation were disintegrated within 30 minutes, and the non-disintegrating agricultural chemical particulate matter was settled.

ベンスルフロンメチル(pKa5.03)6.25部、ジオレイルジメチルアンモニウムクロライド12.5部、炭酸カルシウム62.5部、ベントナイト12.5部を均一に混合した混合物を、衝撃式粉砕機で粉砕した。得られた粉末を高速撹拌機中で、固形分50%を含有するアクリルエマルション12.5部と適量の水を加えて混練したのち、ドーム型造粒機を用い目開き径0.5mmのスクリーンより押出し造粒し、造粒物を60℃で静置乾燥して、ベンスルフロンメチルを6.25質量%含有する、直径0.4〜0.6mm、長さ1〜6mmの農薬粒状物を得た。得られた農薬粒状物を水中に投下し、30分後に粒の崩壊状態を観察したところ、崩壊した粒は認められず、非崩壊型と判定された。  A mixture in which 6.25 parts of bensulfuron methyl (pKa 5.03), 12.5 parts of dioleyldimethylammonium chloride, 62.5 parts of calcium carbonate, and 12.5 parts of bentonite were uniformly mixed was pulverized with an impact pulverizer. . The obtained powder was kneaded in a high-speed stirrer by adding 12.5 parts of an acrylic emulsion containing 50% solids and an appropriate amount of water, and then screened using a dome type granulator. Extruded and granulated, the granulated product was allowed to stand and dried at 60 ° C., and a pesticidal granular material having a diameter of 0.4 to 0.6 mm and a length of 1 to 6 mm containing 6.25% by mass of bensulfuron methyl. Obtained. The obtained agrochemical granular material was dropped into water, and the collapsed state of the particles was observed after 30 minutes. As a result, no collapsed particles were observed, and the particles were determined to be non-disintegrating.

次に、この非崩壊型農薬粒状物32部、エアミルで微粉砕したメフェナセット32部、ジオクチルスルホサクシネート1部、ポリオキシエチレンアセチレングリコール2部、酵素変性デキストリン3部、実施例1で用いたプラスチック中空体12部、ベントナイト5部、無水硫酸ナトリウム10部、尿素13.2部に適量の水を加えた混合物を二軸型ニーダーで混練したのち、押出し造粒機を用い目開き径5mmのスクリーンより押出し造粒し、目標の大きさになるように整粒したのち、品温60℃で流動層乾燥機により乾燥し、篩い分けることにより、直径3〜7mm、長さ3〜20mmのベンスルフロンメチル2質量%、メフェナセット32質量%を含有する粒状物を均一拡散性粒状農薬製剤として得た。得られた均一拡散性粒状農薬製剤を水中に投下し、観察した結果、30分以内で該製剤の粒子が崩壊し、非崩壊型農薬粒状物は沈降した。  Next, 32 parts of this non-disintegrating pesticide granule, 32 parts of mefenaset finely pulverized with an air mill, 1 part of dioctylsulfosuccinate, 2 parts of polyoxyethylene acetylene glycol, 3 parts of enzyme-modified dextrin, plastic used in Example 1 A mixture of 12 parts of hollow body, 5 parts of bentonite, 10 parts of anhydrous sodium sulfate, 13.2 parts of urea and a suitable amount of water is kneaded with a twin screw kneader, and then a screen having an opening diameter of 5 mm using an extrusion granulator. After extruding and granulating, adjusting the size to the target size, drying with a fluidized bed dryer at a product temperature of 60 ° C., and sieving, Bensulfuron with a diameter of 3 to 7 mm and a length of 3 to 20 mm A granular material containing 2% by mass of methyl and 32% by mass of mefenacet was obtained as a uniform diffusible granular agricultural chemical preparation. As a result of dropping and observing the obtained uniformly diffusible granular agricultural chemical formulation in water, the particles of the pharmaceutical formulation were disintegrated within 30 minutes, and the non-disintegrating agricultural chemical particulate matter was settled.

一般式(I)でRがエチル基である化合物(以下化合物Aと称する。pKa6.17)10部、塩基性ホワイトカーボン1.7部を均一に混合し、エアミルで微粉砕した化合物A含有粉末を調製した。Compound A containing 10 parts of general formula (I) wherein R 1 is an ethyl group (hereinafter referred to as Compound A, pKa 6.17) and 1.7 parts of basic white carbon are uniformly mixed and finely pulverized with an air mill A powder was prepared.

円錐スクリュー型混合機に粒度16〜35メッシュ(1000〜425μm)のケイソウ土75部を入れ、混合しながら、別に予めジラウリルジメチルアンモニウムクロライド10部、プロピレングリコール2部、ポリプロピレングリコール(分子量:1000)1.3部をプロペラ式混合機で加温混合して調製したカチオン界面活性剤溶液を投入した。投入終了後直ちに上記化合物A含有粉末を投入し、均一に混合して粒状とし、この粒状物を60℃の棚段乾燥機でエージングし、粒径0.4〜1.1mmの農薬粒状物を得た。得られた農薬粒状物を水中に投下し、30分後に粒の崩壊状態を観察したところ、崩壊した粒は認められず、非崩壊型と判定された。  75 parts of diatomaceous earth having a particle size of 16 to 35 mesh (1000 to 425 μm) is put into a conical screw type mixer, and separately mixed with 10 parts of dilauryldimethylammonium chloride, 2 parts of propylene glycol, and polypropylene glycol (molecular weight: 1000). A cationic surfactant solution prepared by warming and mixing 1.3 parts with a propeller mixer was added. Immediately after the completion of the charging, the compound A-containing powder is charged, uniformly mixed and granulated, and this granulated material is aged with a shelf dryer at 60 ° C. to obtain a pesticide granular material having a particle size of 0.4 to 1.1 mm. Obtained. The obtained agrochemical granular material was dropped into water, and the collapsed state of the particles was observed after 30 minutes. As a result, no collapsed particles were observed, and the particles were determined to be non-disintegrating.

次に、この非崩壊型農薬粒状物30部、ジブチルナフタレンスルホン酸ナトリウム3部、ラウリル硫酸塩2部、ポリオキシエチレンアセチレングリコール3部、酵素変性デキストリン2部、ポリアクリル酸ナトリウム1部、ホワイトカーボン2部、実施例1で用いたプラスチック中空体14部、無水硫酸ナトリウム20部、尿素34.9部に適量の水を加えた混合物を二軸型ニーダーで混練したのち、押出し造粒機を用い目開き径5mmのスクリーンより押出し造粒し、目標の大きさになるように整粒したのち、品温60℃で流動層乾燥機により乾燥し、篩い分けることにより、直径3〜7mm、長さ3〜20mmの化合物A3質量%を含有する粒状物を均一拡散性粒状農薬製剤として得た。得られた均一拡散性粒状農薬製剤を水中に投下し、観察した結果、30分以内で該製剤の粒子が崩壊し、非崩壊型農薬粒状物は沈降した。  Next, 30 parts of this non-disintegrating pesticide granular material, 3 parts of sodium dibutylnaphthalene sulfonate, 2 parts of lauryl sulfate, 3 parts of polyoxyethylene acetylene glycol, 2 parts of enzyme-modified dextrin, 1 part of sodium polyacrylate, white carbon After mixing 2 parts of plastic hollow body used in Example 1, 14 parts of anhydrous sodium sulfate, 20 parts of anhydrous sodium sulfate and 34.9 parts of urea with an appropriate amount of water with a twin screw kneader, an extrusion granulator was used. After extruding and granulating from a screen with an opening diameter of 5 mm, adjusting the size to the target size, drying with a fluidized bed dryer at a product temperature of 60 ° C., and sieving, the diameter is 3 to 7 mm and the length A granular material containing 3% by mass of Compound A of 3 to 20 mm was obtained as a uniformly diffusible granular agricultural chemical preparation. As a result of dropping and observing the obtained uniformly diffusible granular agricultural chemical formulation in water, the particles of the pharmaceutical formulation were disintegrated within 30 minutes, and the non-disintegrating agricultural chemical particulate matter was settled.

化合物A(pKa6.17)7.5部、N−メチル−2−ピロリドン10部、ジオレイルジメチルアンモニウムクロライド10部をプロペラ式混合機で混合し、化合物A含有溶液を調製した。得られた溶液を、1%水懸濁液のpHが7〜10である、粒度16〜35メッシュ(1000〜425μm)の塩基性の酸性白土75部に吸着させ、粒径0.4〜1.1mmの農薬粒状物を得た。得られた農薬粒状物を水中に投下し、30分後に粒の崩壊状態を観察したところ、崩壊した粒は認められず、非崩壊型と判定された。  7.5 parts of compound A (pKa 6.17), 10 parts of N-methyl-2-pyrrolidone, and 10 parts of dioleyldimethylammonium chloride were mixed with a propeller mixer to prepare a compound A-containing solution. The obtained solution was adsorbed on 75 parts of basic acidic clay having a particle size of 16 to 35 mesh (1000 to 425 μm) having a pH of 7 to 1% and a particle size of 0.4 to 1. A 1 mm pesticide granule was obtained. The obtained agrochemical granular material was dropped into water, and the collapsed state of the particles was observed after 30 minutes. As a result, no collapsed particles were observed, and the particles were determined to be non-disintegrating.

次に、この非崩壊型農薬粒状物40部、ジブチルナフタレンスルホン酸ナトリウム3部、ラウリル硫酸塩2部、ポリオキシエチレンアセチレングリコール2部、ポリアクリル酸ナトリウム0.7部、球状中空ガラス[フジバルーン(商品名)、富士シリシア化学株式会社製]20部、無水硫酸ナトリウム15部、尿素17.3部を高速撹拌機中で均一に混合し、適量の水を加えて混練したのち、得られた混合物を、バスケット型造粒機を用い目開き径5mmのスクリーンより押出し造粒し、目標の大きさになるように整粒したのち、品温60℃で流動層乾燥機により乾燥し、篩い分けることにより、直径3〜7mm、長さ3〜20mmの化合物A3質量%を含有する粒状物を均一拡散性粒状農薬製剤として得た。得られた均一拡散性粒状農薬製剤を水中に投下し、観察した結果、30分以内で該製剤の粒子が崩壊し、非崩壊型農薬粒状物は沈降した。  Next, 40 parts of this non-disintegrating agrochemical granule, 3 parts of sodium dibutylnaphthalenesulfonate, 2 parts of lauryl sulfate, 2 parts of polyoxyethylene acetylene glycol, 0.7 part of sodium polyacrylate, spherical hollow glass [Fuji Balloon (Trade name), manufactured by Fuji Silysia Chemical Ltd.] 20 parts, 15 parts of anhydrous sodium sulfate, and 17.3 parts of urea were uniformly mixed in a high-speed stirrer, and kneaded after adding an appropriate amount of water. The mixture is extruded and granulated using a basket-type granulator from a screen having an opening diameter of 5 mm, and sized to the target size, dried at a product temperature of 60 ° C. with a fluidized bed dryer, and sieved. Thus, a granular material containing 3% by mass of Compound A having a diameter of 3 to 7 mm and a length of 3 to 20 mm was obtained as a uniformly diffusible granular agricultural chemical preparation. As a result of dropping and observing the obtained uniformly diffusible granular agricultural chemical formulation in water, the particles of the pharmaceutical formulation were disintegrated within 30 minutes, and the non-disintegrating agricultural chemical particulate matter was settled.

一般式(I)でRがメトキシメチル基である化合物(以下化合物Bと称する。pKa5.75)10部、ジステアリルジメチルアンモニウムクロライド6.7部、ジラウリルジメチルアンモニウムクロライド6.7部、炭酸カルシウム63.2部、ポリビニルアルコール6.7部、α化でんぷん6.7部を均一に混合した混合物を、衝撃式粉砕機で粉砕した。得られた粉末に適量の水を加えた混合物を高速撹拌機で混練したのち、ドーム型造粒機を用い目開き径0.5mmのスクリーンより押出し造粒し、造粒物を60℃で静置乾燥して、化合物Bを10質量%含有する、直径0.4〜0.6mm、長さ1〜6mmの農薬粒状物を得た。得られた農薬粒状物を水中に投下し、30分後に粒の崩壊状態を観察したところ、崩壊した粒は認められず、非崩壊型と判定された。A compound of the general formula (I) wherein R 1 is a methoxymethyl group (hereinafter referred to as Compound B, pKa 5.75), 6.7 parts of distearyldimethylammonium chloride, 6.7 parts of dilauryldimethylammonium chloride, carbonic acid A mixture obtained by uniformly mixing 63.2 parts of calcium, 6.7 parts of polyvinyl alcohol, and 6.7 parts of pregelatinized starch was pulverized with an impact pulverizer. A mixture obtained by adding an appropriate amount of water to the obtained powder is kneaded with a high-speed stirrer, and then extruded and granulated using a dome-type granulator through a screen having an aperture diameter of 0.5 mm. After drying, an agrochemical granule containing 10% by mass of Compound B and having a diameter of 0.4 to 0.6 mm and a length of 1 to 6 mm was obtained. The obtained agrochemical granular material was dropped into water, and the collapsed state of the particles was observed after 30 minutes. As a result, no collapsed particles were observed, and the particles were determined to be non-disintegrating.

次に、この非崩壊型農薬粒状物30部、ポリオキシエチレンアセチレングリコール1部、ポリオキシエチレンポリオキシプロピレンブロックポリマー2部、ポリオキシエチレンスチリルフェニルエーテルリン酸アミン塩3部、酵素変性デキストリン3部、実施例1で用いたプラスチック中空体14部、ベントナイト5部、無水硫酸ナトリウム20部、尿素30.9部に適量の水を加えた混合物を二軸型ニーダーで混練したのち、押出し造粒機を用い目開き径5mmのスクリーンより押出し造粒し、目標の大きさになるように整粒したのち、品温60℃で流動層乾燥機により乾燥し、篩い分けることにより、直径3〜7mm、長さ3〜20mmの化合物B3質量%を含有する粒状物を均一拡散性粒状農薬製剤として得た。得られた均一拡散性粒状農薬製剤を水中に投下し、観察した結果、30分以内で該製剤の粒子が崩壊し、非崩壊型農薬粒状物は沈降した。  Next, 30 parts of this non-disintegrating pesticide particulate, 1 part of polyoxyethylene acetylene glycol, 2 parts of polyoxyethylene polyoxypropylene block polymer, 3 parts of polyoxyethylene styrylphenyl ether phosphate amine salt, 3 parts of enzyme-modified dextrin A mixture of 14 parts of hollow plastic body used in Example 1, 5 parts of bentonite, 20 parts of anhydrous sodium sulfate and 30.9 parts of urea with an appropriate amount of water was kneaded with a twin-screw kneader, and then an extrusion granulator After extruding and granulating from a screen with an opening diameter of 5 mm using a sizing and sizing to a target size, drying with a fluidized bed dryer at a product temperature of 60 ° C., and sieving, a diameter of 3 to 7 mm, A granular material containing 3% by mass of Compound B having a length of 3 to 20 mm was obtained as a uniformly diffusible granular agricultural chemical preparation. As a result of dropping and observing the obtained uniformly diffusible granular agricultural chemical formulation in water, the particles of the pharmaceutical formulation were disintegrated within 30 minutes, and the non-disintegrating agricultural chemical particulate matter was settled.

化合物B(pKa5.75)6.25部、ジステアリルジメチルアンモニウムクロライド12.5部、炭酸カルシウム62.5部、ベントナイト12.5部を均一に混合した混合物を、衝撃式粉砕機で粉砕した。得られた粉末にアクリルエマルション6.25部と適量の水を加えた混合物を高速撹拌機で混練したのち、ドーム型造粒機を用い目開き径0.5mmのスクリーンより押出し造粒し、造粒物を60℃で静置乾燥して、化合物Bを6.25質量%含有する、直径0.4〜0.6mm、長さ1〜6mmの農薬粒状物を得た。得られた農薬粒状物を水中に投下し、30分後に粒の崩壊状態を観察したところ、崩壊した粒は認められず、非崩壊型と判定された。  A mixture in which 6.25 parts of Compound B (pKa 5.75), 12.5 parts of distearyldimethylammonium chloride, 62.5 parts of calcium carbonate, and 12.5 parts of bentonite were uniformly mixed was pulverized with an impact pulverizer. A mixture obtained by adding 6.25 parts of an acrylic emulsion and an appropriate amount of water to the obtained powder is kneaded with a high-speed stirrer, and then extruded and granulated from a screen having an aperture diameter of 0.5 mm using a dome-type granulator. The granules were left to dry at 60 ° C. to obtain agricultural chemical granules containing 6.25% by mass of Compound B and having a diameter of 0.4 to 0.6 mm and a length of 1 to 6 mm. The obtained agrochemical granular material was dropped into water, and the collapsed state of the particles was observed after 30 minutes. As a result, no collapsed particles were observed, and the particles were determined to be non-disintegrating.

次に、この非崩壊型農薬粒状物32部、エアミルで微粉砕した化合物B1部、ポリオキシエチレンアセチレングリコール1部、ポリオキシエチレンポリオキシプロピレンブロックポリマー2部、ポリオキシエチレンスチリルフェニルエーテルリン酸アミン塩3部、酵素変性デキストリン3部、実施例1で用いたプラスチック中空体14部、ベントナイト5部、無水硫酸ナトリウム20部、尿素30.9部に適量の水を加えた混合物を二軸型ニーダーで混練したのち、押出し造粒機を用い目開き径5mmのスクリーンより押出し造粒し、目標の大きさになるように整粒したのち、品温60℃で流動層乾燥機により乾燥し、篩い分けることにより、直径3〜7mm、長さ3〜20mmの化合物B3質量%を含有する粒状物を均一拡散性粒状農薬製剤として得た。得られた均一拡散性粒状農薬製剤を水中に投下し、観察した結果、30分以内で該製剤の粒子が崩壊し、非崩壊型農薬粒状物は沈降した。  Next, 32 parts of this non-disintegrating agrochemical granule, 1 part of compound B finely pulverized with an air mill, 1 part of polyoxyethylene acetylene glycol, 2 parts of polyoxyethylene polyoxypropylene block polymer, polyoxyethylene styryl phenyl ether phosphate amine A biaxial kneader containing a mixture of 3 parts of salt, 3 parts of enzyme-modified dextrin, 14 parts of plastic hollow body used in Example 1, 5 parts of bentonite, 20 parts of anhydrous sodium sulfate, 30.9 parts of urea and 30.9 parts of urea After being kneaded, the mixture is extruded and granulated from a screen having an opening diameter of 5 mm using an extrusion granulator, sized to the target size, dried at a product temperature of 60 ° C. with a fluidized bed dryer, and sieved. By dividing, a granular material containing 3% by mass of compound B having a diameter of 3 to 7 mm and a length of 3 to 20 mm is made of a uniform diffusible granular agricultural chemical. It was obtained as a. As a result of dropping and observing the obtained uniformly diffusible granular agricultural chemical formulation in water, the particles of the pharmaceutical formulation were disintegrated within 30 minutes, and the non-disintegrating agricultural chemical particulate matter was settled.

化合物B(pKa5.75)10部、ジステアリルジメチルアンモニウムクロライド13.3部、炭酸カルシウム56.9部、ベントナイト13.3部を均一に混合した混合物を、衝撃式粉砕機で粉砕した。得られた粉末に固形分50%を含有するアクリルエマルション13部と適量の水を加えた混合物を高速撹拌機で、混練したのち、ドーム型造粒機を用い目開き径0.5mmのスクリーンより押出し造粒し、造粒物を60℃で静置乾燥して、化合物Bを10質量%含有する、直径0.4〜0.6mm、長さ1〜6mmの農薬粒状物を得た。得られた農薬粒状物を水中に投下し、30分後に粒の崩壊状態を観察したところ、崩壊した粒は認められず、非崩壊型と判定された。  A mixture in which 10 parts of Compound B (pKa 5.75), 13.3 parts of distearyldimethylammonium chloride, 56.9 parts of calcium carbonate, and 13.3 parts of bentonite were uniformly mixed was pulverized with an impact pulverizer. A mixture obtained by adding 13 parts of an acrylic emulsion containing a solid content of 50% and an appropriate amount of water to the obtained powder was kneaded with a high-speed stirrer, and then screened from a screen having an aperture diameter of 0.5 mm using a dome type granulator. Extrusion granulation was performed, and the granulated product was allowed to stand and dry at 60 ° C. to obtain an agrochemical granular material containing 10% by mass of Compound B and having a diameter of 0.4 to 0.6 mm and a length of 1 to 6 mm. The obtained agrochemical granular material was dropped into water, and the collapsed state of the particles was observed after 30 minutes. As a result, no collapsed particles were observed, and the particles were determined to be non-disintegrating.

次に、この非崩壊型農薬粒状物30部、エアミルで微粉砕したフェントラザミド8部、ジブチルナフタレンスルホン酸ナトリウム5部、ラウリル硫酸塩1部、ポリオキシエチレンアセチレングリコール3部、酵素変性デキストリン2部、ポリアクリル酸ナトリウム0.5部、実施例1で用いたプラスチック中空体14部、無水硫酸ナトリウム20部、尿素28.4部に適量の水を加えた混合物を二軸型ニーダーで混練したのち、押出し造粒機を用い目開き径5mmのスクリーンより押出し造粒し、目標の大きさになるように整粒したのち、品温60℃で流動層乾燥機により乾燥し、篩い分けることにより、直径3〜7mm、長さ3〜20mmの化合物B3質量%、フェントラザミド8質量%を含有する粒状物を均一拡散性粒状農薬製剤として得た。得られた均一拡散性粒状農薬製剤を水中に投下し、観察した結果、30分以内で該製剤の粒子が崩壊し、非崩壊型農薬粒状物は沈降した。  Next, 30 parts of this non-disintegrating pesticide particulate, 8 parts of fentrazamide finely pulverized with an air mill, 5 parts of sodium dibutylnaphthalenesulfonate, 1 part of lauryl sulfate, 3 parts of polyoxyethylene acetylene glycol, 2 parts of enzyme-modified dextrin, After kneading a mixture of 0.5 parts of sodium polyacrylate, 14 parts of the hollow plastic body used in Example 1, 20 parts of anhydrous sodium sulfate, and 28.4 parts of urea with an appropriate amount of water using a twin-screw kneader, After extruding and granulating from a screen with an opening diameter of 5 mm using an extrusion granulator, adjusting the size to the target size, drying with a fluidized bed dryer at a product temperature of 60 ° C, and sieving, 3 to 7 mm, 3 to 20 mm in length as a uniform diffusible granular agricultural chemical preparation containing 3% by mass of Compound B and 8% by mass of phentolazamide It was. As a result of dropping and observing the obtained uniformly diffusible granular agricultural chemical formulation in water, the particles of the pharmaceutical formulation were disintegrated within 30 minutes, and the non-disintegrating agricultural chemical particulate matter was settled.

ピラゾスルフロンエチル(pKa3.91)6.25部、セチルトリメチルアンモニウムクロライド6.25部、炭酸カルシウム68.75部、ポリビニルアルコール18.75部を均一に混合した混合物を、衝撃式粉砕機で粉砕した。得られた粉末を高速撹拌機中で適量の水を加えて混練したのち、ドーム型造粒機を用い目開き径0.5mmのスクリーンより押出し造粒し、造粒物を60℃で静置乾燥して、ピラゾスルフロンエチルを6.25質量%含有する、直径0.4〜0.6mm、長さ1〜6mmの農薬粒状物を得た。この農薬粒状物を水中に投下し、30分後に粒の崩壊状態を観察したところ、崩壊した粒は認められず、非崩壊型と判定された。  A mixture obtained by uniformly mixing 6.25 parts of pyrazosulfuron ethyl (pKa 3.91), 6.25 parts of cetyltrimethylammonium chloride, 68.75 parts of calcium carbonate, and 18.75 parts of polyvinyl alcohol is pulverized with an impact pulverizer. did. The obtained powder was kneaded with an appropriate amount of water in a high-speed stirrer, and then extruded and granulated from a screen having an aperture diameter of 0.5 mm using a dome type granulator, and the granulated product was allowed to stand at 60 ° C. It dried and obtained the agrochemical granular material of diameter 0.4-0.6mm and length 1-6mm containing 6.25 mass% of pyrazosulfuron ethyl. When this pesticide granular material was dropped into water and the state of particle disintegration was observed 30 minutes later, no disintegrated particles were observed, and it was determined to be non-disintegrating.

次に、この非崩壊型農薬粒状物16部、ブチルナフタレンスルホン酸ホルマリン縮合物ナトリウム塩5部、ポリオキシエチレンアセチレングリコール1部、ポリアクリル酸ナトリウム0.5部、実施例1で用いたプラスチック中空体14部、無水硫酸ナトリウム20部、尿素55.4部に適量の水を加えた混合物を高速撹拌機中で混練したのち、押出し造粒機を用い目開き径5mmのスクリーンより押出し造粒し、目標の大きさになるように整粒したのち、品温60℃で流動層乾燥機により乾燥し、篩い分けることにより、直径3〜7mm、長さ3〜20mmのピラゾスルフロンエチル1質量%を含有する粒状物を均一拡散性粒状農薬製剤として得た。得られた均一拡散性粒状農薬製剤を水中に投下し、観察した結果、30分以内で該製剤の粒子が崩壊し、非崩壊型農薬粒状物は沈降した。  Next, 16 parts of this non-disintegrating agrochemical granular material, 5 parts of sodium salt of butylnaphthalenesulfonic acid formalin condensate, 1 part of polyoxyethylene acetylene glycol, 0.5 part of sodium polyacrylate, and the plastic hollow used in Example 1 A mixture of 14 parts of the body, 20 parts of anhydrous sodium sulfate and 55.4 parts of urea with an appropriate amount of water was kneaded in a high-speed stirrer, and then extruded and granulated from a screen having an opening diameter of 5 mm using an extrusion granulator. After adjusting the particle size to the target size, it is dried with a fluidized bed dryer at a product temperature of 60 ° C., and sieved to 1% by mass of pyrazosulfuron ethyl having a diameter of 3 to 7 mm and a length of 3 to 20 mm. Was obtained as a uniformly diffusible granular agrochemical formulation. As a result of dropping and observing the obtained uniformly diffusible granular agricultural chemical formulation in water, the particles of the pharmaceutical formulation were disintegrated within 30 minutes, and the non-disintegrating agricultural chemical particulate matter was settled.

トリシクラゾール(pKa1.6)20部、ジステアリルジメチルアンモニウムクロライド15部、炭酸カルシウム55部、ポリビニルアルコール10部を均一に混合した混合物を、衝撃式粉砕機で粉砕した。得られた粉末を高速撹拌機中で適量の水を加えて混練したのち、ドーム型造粒機を用い目開き径0.7mmのスクリーンより押出し造粒し、造粒物を60℃で静置乾燥して、トリシクラゾールを20質量%含有する、直径0.6〜0.8mm、長さ2〜9mmの農薬粒状物を得た。得られた農薬粒状物を水中に投下し、30分後に粒の崩壊状態を観察したところ、崩壊した粒は認められず、非崩壊型と判定された。  A mixture obtained by uniformly mixing 20 parts of tricyclazole (pKa 1.6), 15 parts of distearyldimethylammonium chloride, 55 parts of calcium carbonate, and 10 parts of polyvinyl alcohol was pulverized with an impact pulverizer. The obtained powder was kneaded with an appropriate amount of water in a high-speed stirrer, and then extruded and granulated from a screen having an aperture diameter of 0.7 mm using a dome type granulator, and the granulated product was allowed to stand at 60 ° C. It dried and obtained the agrochemical granular material of diameter 0.6-0.8mm and length 2-9mm containing 20 mass% of tricyclazole. The obtained agrochemical granular material was dropped into water, and the collapsed state of the particles was observed after 30 minutes. As a result, no collapsed particles were observed, and the particles were determined to be non-disintegrating.

次に、この非崩壊型農薬粒状物40部、ブチルナフタレンスルホン酸ホルマリン縮合物ナトリウム塩5部、ポリオキシエチレンアセチレングリコール1部、ポリアクリル酸ナトリウム0.5部、プラスチック中空体であるアクリロニトリル系プラスチックバルーン[マツモトマイクロスフェアーF−80E(商品名)、松本油脂製薬株式会社製]14部、無水硫酸ナトリウム20部、尿素31.4部に適量の水を加えた混合物を高速撹拌機で混練したのち、押出し造粒機を用い目開き径5mmのスクリーンより押出し造粒し、目標の大きさになるように整粒したのち、品温60℃で流動層乾燥機により乾燥し、篩い分けることにより、直径3〜7mm、長さ3〜20mmのトリシクラゾール8質量%を含有する粒状物を均一拡散性粒状農薬製剤として得た。得られた均一拡散性粒状農薬製剤を水中に投下し、観察した結果、30分以内で該製剤の粒子が崩壊し、非崩壊型農薬粒状物は沈降した。  Next, 40 parts of this non-disintegrating agrochemical granular material, 5 parts of sodium salt of butylnaphthalenesulfonic acid formalin condensate, 1 part of polyoxyethylene acetylene glycol, 0.5 part of sodium polyacrylate, acrylonitrile plastic which is a plastic hollow body Balloon [Matsumoto Microsphere F-80E (trade name), manufactured by Matsumoto Yushi Seiyaku Co., Ltd.] 14 parts, 20 parts of anhydrous sodium sulfate and 31.4 parts of urea were kneaded with a high-speed stirrer. After that, it is extruded and granulated from a screen with an opening diameter of 5 mm using an extrusion granulator, sized to the target size, dried with a fluidized bed dryer at a product temperature of 60 ° C., and sieved. Made of a uniform diffusible granular agricultural chemical containing 8% by mass of tricyclazole having a diameter of 3 to 7 mm and a length of 3 to 20 mm It was obtained as a. As a result of dropping and observing the obtained uniformly diffusible granular agricultural chemical formulation in water, the particles of the pharmaceutical formulation were disintegrated within 30 minutes, and the non-disintegrating agricultural chemical particulate matter was settled.

PHC(pKa11.6)20部、ジステアリルジメチルアンモニウムクロライド15部、炭酸カルシウム55部、ポリビニルアルコール10部を均一に混合した混合物を、衝撃式粉砕機で粉砕した。得られた粉末に適量の水を加えた混合物を高速撹拌機で混練したのち、ドーム型造粒機を用い目開き径0.7mmのスクリーンより押出し造粒し、造粒物を60℃で静置乾燥して、PHCを20質量%含有する、直径0.6〜0.8mm、長さ2〜9mmの農薬粒状物を得た。得られた農薬粒状物を水中に投下し、30分後に粒の崩壊状態を観察したところ、崩壊した粒は認められず、非崩壊型と判定された。  A mixture in which 20 parts of PHC (pKa 11.6), 15 parts of distearyldimethylammonium chloride, 55 parts of calcium carbonate and 10 parts of polyvinyl alcohol were uniformly mixed was pulverized with an impact pulverizer. A mixture obtained by adding an appropriate amount of water to the obtained powder is kneaded with a high-speed stirrer, and then extruded and granulated from a screen having an aperture diameter of 0.7 mm using a dome type granulator. After drying, an agrochemical granule containing 20% by mass of PHC and having a diameter of 0.6 to 0.8 mm and a length of 2 to 9 mm was obtained. The obtained agrochemical granular material was dropped into water, and the collapsed state of the particles was observed after 30 minutes. As a result, no collapsed particles were observed, and the particles were determined to be non-disintegrating.

次に、この非崩壊型農薬粒状物40部、ブチルナフタレンスルホン酸ホルマリン縮合物ナトリウム塩5部、ポリオキシエチレンアセチレングリコール1部、ポリアクリル酸ナトリウム0.5部、実施例9で用いたプラスチック中空体14部、無水硫酸ナトリウム20部、尿素31.4部に適量の水を加えた混合物を高速撹拌機で混練したのち、押出し造粒機を用い目開き径5mmのスクリーンより押出し造粒し、目標の大きさになるように整粒したのち、品温60℃で流動層乾燥機により乾燥し、篩い分けることにより、直径3〜7mm、長さ3〜20mmのPHC8質量%を含有する粒状物を均一拡散性粒状農薬製剤として得た。得られた均一拡散性粒状農薬製剤を水中に投下し、観察した結果、30分以内で該製剤の粒子が崩壊し、非崩壊型農薬粒状物は沈降した。  Next, 40 parts of this non-disintegrating agrochemical granule, 5 parts of sodium salt of butylnaphthalene sulfonic acid formalin condensate, 1 part of polyoxyethylene acetylene glycol, 0.5 part of sodium polyacrylate, hollow plastic used in Example 9 After kneading a mixture of 14 parts of the body, 20 parts of anhydrous sodium sulfate and 31.4 parts of urea with an appropriate amount of water with a high-speed stirrer, the mixture is extruded and granulated from a screen having an opening diameter of 5 mm using an extrusion granulator, Granules containing 8% by mass of PHC having a diameter of 3 to 7 mm and a length of 3 to 20 mm by sieving to a target size, drying with a fluidized bed dryer at a product temperature of 60 ° C., and sieving. Was obtained as a uniform diffusible granular pesticide formulation. As a result of dropping and observing the obtained uniformly diffusible granular agricultural chemical formulation in water, the particles of the pharmaceutical formulation were disintegrated within 30 minutes, and the non-disintegrating agricultural chemical particulate matter was settled.

比較例1
ベンスルフロンメチル(pKa5.03)6.25部、炭酸カルシウム81.25部、ポリビニルアルコール6.25部、α化でんぷん6.25部を均一に混合した混合物を、衝撃式粉砕機で粉砕した。得られた粉末に適量の水を加えた混合物を高速撹拌機で混練したのち、ドーム型造粒機を用い目開き径0.5mmのスクリーンより押出し造粒し、造粒物を60℃で静置乾燥して、ベンスルフロンメチルを6.25質量%含有する、直径0.4〜0.6mm、長さ1〜6mmの農薬粒状物を得た。得られた農薬粒状物を水中に投下し、30分後に粒の崩壊状態を観察したところ、崩壊した粒は認められず、非崩壊型と判定された。
Comparative Example 1
A mixture in which 6.25 parts of bensulfuron methyl (pKa 5.03), 81.25 parts of calcium carbonate, 6.25 parts of polyvinyl alcohol, and 6.25 parts of pregelatinized starch were uniformly mixed was pulverized with an impact pulverizer. A mixture obtained by adding an appropriate amount of water to the obtained powder is kneaded with a high-speed stirrer, and then extruded and granulated using a dome-type granulator through a screen having an aperture diameter of 0.5 mm. After drying, an agrochemical granule having a diameter of 0.4 to 0.6 mm and a length of 1 to 6 mm containing 6.25% by mass of bensulfuron methyl was obtained. The obtained agrochemical granular material was dropped into water, and the collapsed state of the particles was observed after 30 minutes. As a result, no collapsed particles were observed, and the particles were determined to be non-disintegrating.

次に、この非崩壊型農薬粒状物32部、ポリオキシエチレンアセチレングリコール3部、酵素変性デキストリン2部、実施例1で用いたプラスチック中空体14部、無水硫酸ナトリウム20部、尿素40.9部に適量の水を加えた混合物を二軸型ニーダーで混練したのち、押出し造粒機を用い目開き径5mmのスクリーンより押出し造粒し、目標の大きさになるように整粒したのち、品温60℃で流動層乾燥機により乾燥し、篩い分けることにより、直径3〜7mm、長さ3〜20mmのベンスルフロンメチル2質量%を含有する粒状物を均一拡散性粒状農薬製剤として得た。得られた均一拡散性粒状農薬製剤を水中に投下し、観察した結果、30分以内で該製剤の粒子が崩壊し、非崩壊型農薬粒状物は沈降した。  Next, 32 parts of this non-disintegrating agrochemical granule, 3 parts of polyoxyethylene acetylene glycol, 2 parts of enzyme-modified dextrin, 14 parts of hollow plastic body used in Example 1, 20 parts of anhydrous sodium sulfate, 40.9 parts of urea After kneading a mixture with a suitable amount of water in a twin-screw kneader, the mixture is extruded and granulated from a screen with an opening diameter of 5 mm using an extrusion granulator, and the particles are sized to the target size. By drying with a fluidized bed dryer at a temperature of 60 ° C. and sieving, a granular material containing 2% by mass of bensulfuron methyl having a diameter of 3 to 7 mm and a length of 3 to 20 mm was obtained as a uniform diffusible granular agricultural chemical preparation. As a result of dropping and observing the obtained uniformly diffusible granular agricultural chemical formulation in water, the particles of the pharmaceutical formulation were disintegrated within 30 minutes, and the non-disintegrating agricultural chemical particulate matter was settled.

比較例2
化合物A(pKa6.17)10部、塩基性ホワイトカーボン1.7部を均一に混合し、エアミルで微粉砕して化合物A含有粉末を調製した。
Comparative Example 2
Compound A (pKa 6.17) 10 parts and basic white carbon 1.7 parts were mixed uniformly and pulverized with an air mill to prepare Compound A-containing powder.

円錐スクリュー型混合機に粒度16〜35メッシュ(1000〜425μm)のケイソウ土粒75部を入れ、混合しながら、別に予めプロピレングリコール12部、ポリプロピレングリコール(分子量:1000)1.3部をプロペラ式混合機で加温混合して調製した溶液を投入した。投入終了後直ちに上記化合物A含有粉末を投入し、均一に混合して粒状とし、この粒状物を60℃の棚段乾燥機でエージングし、粒径0.4〜1.1mmの農薬粒状物を得た。この農薬粒状物を水中に投下し、30分後に粒の崩壊状態を観察したところ、崩壊した粒は認められず、非崩壊型と判定された。  75 parts of diatomaceous earth with a particle size of 16 to 35 mesh (1000 to 425 μm) are put into a conical screw type mixer, and while mixing, 12 parts of propylene glycol and 1.3 parts of polypropylene glycol (molecular weight: 1000) are propeller type. A solution prepared by warm mixing with a mixer was added. Immediately after the completion of the charging, the compound A-containing powder is charged, uniformly mixed and granulated, and this granulated material is aged with a shelf dryer at 60 ° C. to obtain a pesticide granular material having a particle size of 0.4 to 1.1 mm. Obtained. When this pesticide granular material was dropped into water and the state of particle disintegration was observed 30 minutes later, no disintegrated particles were observed, and it was determined to be non-disintegrating.

次に、この非崩壊型農薬粒状物30部、ジブチルナフタレンスルホン酸ナトリウム3部、ラウリル硫酸塩2部、ポリオキシエチレンアセチレングリコール3部、酵素変性デキストリン2部、ポリアクリル酸ナトリウム1部、ホワイトカーボン2部、実施例1で用いたプラスチック中空体14部、無水硫酸ナトリウム20部、尿素34.9部に適量の水を加えた混合物を二軸型ニーダーで混練したのち、押出し造粒機を用い目開き径5mmのスクリーンより押出し造粒し、目標の大きさになるように整粒したのち、品温60℃で流動層乾燥機により乾燥し、篩い分けることにより、直径3〜7mm、長さ3〜20mmの化合物A3質量%を含有する粒状物を均一拡散性粒状農薬製剤として得た。得られた均一拡散性粒状農薬製剤を水中に投下し、観察した結果、30分以内で該製剤の粒子が崩壊し、非崩壊型農薬粒状物は沈降した。  Next, 30 parts of this non-disintegrating pesticide granular material, 3 parts of sodium dibutylnaphthalene sulfonate, 2 parts of lauryl sulfate, 3 parts of polyoxyethylene acetylene glycol, 2 parts of enzyme-modified dextrin, 1 part of sodium polyacrylate, white carbon After mixing 2 parts of plastic hollow body used in Example 1, 14 parts of anhydrous sodium sulfate, 20 parts of anhydrous sodium sulfate and 34.9 parts of urea with an appropriate amount of water with a twin screw kneader, an extrusion granulator was used. After extruding and granulating from a screen with an opening diameter of 5 mm, adjusting the size to the target size, drying with a fluidized bed dryer at a product temperature of 60 ° C., and sieving, the diameter is 3 to 7 mm and the length A granular material containing 3% by mass of Compound A of 3 to 20 mm was obtained as a uniformly diffusible granular agricultural chemical preparation. As a result of dropping and observing the obtained uniformly diffusible granular agricultural chemical formulation in water, the particles of the pharmaceutical formulation were disintegrated within 30 minutes, and the non-disintegrating agricultural chemical particulate matter was settled.

比較例3
化合物B(pKa5.75)10部、ジステアリルジメチルアンモニウムクロライド6.7部、ジラウリルジメチルアンモニウムクロライド6.7部、クレー63.2部、ポリビニルアルコール6.7部、α化でんぷん6.7部を均一に混合した混合物を、衝撃式粉砕機で粉砕した。得られた粉末に適量の水を加えた混合物を高速撹拌機で混練したのち、ドーム型造粒機を用い目開き径0.5mmのスクリーンより押出し造粒し、造粒物を60℃で静置乾燥して、化合物Bを10質量%含有する、直径0.4〜0.6mm、長さ1〜6mmの農薬粒状物を得た。この農薬粒状物を水中に投下し、30分後に粒の崩壊状態を観察したところ、崩壊した粒は認められず、非崩壊型と判定された。
Comparative Example 3
Compound B (pKa 5.75) 10 parts, distearyldimethylammonium chloride 6.7 parts, dilauryldimethylammonium chloride 6.7 parts, clay 63.2 parts, polyvinyl alcohol 6.7 parts, pregelatinized starch 6.7 parts The mixture in which the mixture was uniformly mixed was pulverized with an impact pulverizer. A mixture obtained by adding an appropriate amount of water to the obtained powder is kneaded with a high-speed stirrer, and then extruded and granulated using a dome-type granulator through a screen having an aperture diameter of 0.5 mm. After drying, an agrochemical granule containing 10% by mass of Compound B and having a diameter of 0.4 to 0.6 mm and a length of 1 to 6 mm was obtained. When this pesticide granular material was dropped into water and the state of particle disintegration was observed 30 minutes later, no disintegrated particles were observed, and it was determined to be non-disintegrating.

次に、この非崩壊型農薬粒状物30部、ポリオキシエチレンアセチレングリコール1部、ポリオキシエチレンポリオキシプロピレンブロックポリマー2部、ポリオキシエチレンスチリルフェニルエーテルリン酸アミン塩3部、酵素変性デキストリン3部、実施例1で用いたプラスチック中空体14部、無水硫酸ナトリウム20部、尿素38.9部に適量の水を加えた混合物を二軸型ニーダーで混練したのち、押出し造粒機を用い目開き径5mmのスクリーンより押出し造粒し、目標の大きさになるように整粒したのち、品温60℃で流動層乾燥機により乾燥し、篩い分けることにより、直径3〜7mm、長さ3〜20mmの化合物B3質量%含有する粒状物を均一拡散性粒状農薬製剤として得た。得られた均一拡散性粒状農薬製剤を水中に投下し、観察した結果、30分以内で該製剤の粒子が崩壊し、非崩壊型農薬粒状物は沈降した。  Next, 30 parts of this non-disintegrating pesticide particulate, 1 part of polyoxyethylene acetylene glycol, 2 parts of polyoxyethylene polyoxypropylene block polymer, 3 parts of polyoxyethylene styrylphenyl ether phosphate amine salt, 3 parts of enzyme-modified dextrin A mixture of a plastic hollow body used in Example 1, 14 parts of anhydrous sodium sulfate, 20 parts of anhydrous sodium sulfate and 38.9 parts of urea with an appropriate amount of water was kneaded with a twin-screw kneader and then opened using an extrusion granulator. After extruding and granulating from a screen with a diameter of 5 mm, adjusting the size to the target size, drying with a fluidized bed dryer at a product temperature of 60 ° C., and sieving, a diameter of 3 to 7 mm and a length of 3 to 3 A granular material containing 3% by mass of Compound B of 20 mm was obtained as a uniformly diffusible granular agricultural chemical preparation. As a result of dropping and observing the obtained uniformly diffusible granular agricultural chemical formulation in water, the particles of the pharmaceutical formulation were disintegrated within 30 minutes, and the non-disintegrating agricultural chemical particulate matter was settled.

比較例4
ピラゾスルフロンエチル(pKa3.91)6.25部、パラフィン(融点68〜70℃)12部、炭酸カルシウム63.75部、ポリビニルアルコール18部を均一に混合した混合物を、衝撃式粉砕機で粉砕した。得られた粉末に適量の水を加えた混合物を高速撹拌機で混練したのち、ドーム型造粒機を用い目開き径0.5mmのスクリーンより押出し造粒し、造粒物を70℃で静置乾燥して、ピラゾスルフロンエチルを6.25質量%含有する、直径0.4〜0.6mm、長さ1〜6mmの農薬粒状物を得た。得られた農薬粒状物を水中に投下し、30分後に粒の崩壊状態を観察したところ、崩壊した粒は認められず、非崩壊型と判定された。
Comparative Example 4
A mixture in which 6.25 parts of pyrazosulfuron ethyl (pKa 3.91), 12 parts of paraffin (melting point: 68 to 70 ° C.), 63.75 parts of calcium carbonate and 18 parts of polyvinyl alcohol are uniformly mixed is pulverized with an impact pulverizer. did. A mixture obtained by adding an appropriate amount of water to the obtained powder is kneaded with a high-speed stirrer, and then extruded and granulated using a dome-type granulator through a screen having an aperture diameter of 0.5 mm. After drying, an agrochemical granule having a diameter of 0.4 to 0.6 mm and a length of 1 to 6 mm containing 6.25% by mass of pyrazosulfuronethyl was obtained. The obtained agrochemical granular material was dropped into water, and the collapsed state of the particles was observed after 30 minutes. As a result, no collapsed particles were observed, and the particles were determined to be non-disintegrating.

次に、この非崩壊型農薬粒状物16部、ブチルナフタレンスルホン酸ホルマリン縮合物ナトリウム塩5部、ポリオキシエチレンアセチレングリコール1部、ポリアクリル酸ナトリウム0.5部、実施例1で用いたプラスチック中空体14部、無水硫酸ナトリウム20部、尿素55.4部に適量の水を加えた混合物を高速撹拌機で混練したのち、押出し造粒機を用い目開き径5mmのスクリーンより押出し造粒し、目標の大きさになるように整粒したのち、品温60℃で流動層乾燥機により乾燥し、篩い分けることにより、直径3〜7mm、長さ3〜20mmのピラゾスルフロンエチル1質量%を含有する粒状物を均一拡散性粒状農薬製剤として得た。得られた均一拡散性粒状農薬製剤を水中に投下し、観察した結果、30分以内で該製剤の粒子が崩壊し、非崩壊型農薬粒状物は沈降した。  Next, 16 parts of this non-disintegrating agrochemical granular material, 5 parts of sodium salt of butylnaphthalenesulfonic acid formalin condensate, 1 part of polyoxyethylene acetylene glycol, 0.5 part of sodium polyacrylate, and the plastic hollow used in Example 1 After kneading a mixture of 14 parts of a body, 20 parts of anhydrous sodium sulfate and 55.4 parts of urea with an appropriate amount of water with a high-speed stirrer, the mixture is extruded and granulated from a screen having an opening diameter of 5 mm using an extrusion granulator, After sizing to the target size, drying with a fluidized bed drier at a product temperature of 60 ° C. and sieving, 1% by mass of pyrazosulfuron ethyl having a diameter of 3 to 7 mm and a length of 3 to 20 mm is obtained. The contained granular material was obtained as a uniform diffusible granular agricultural chemical formulation. As a result of dropping and observing the obtained uniformly diffusible granular agricultural chemical formulation in water, the particles of the pharmaceutical formulation were disintegrated within 30 minutes, and the non-disintegrating agricultural chemical particulate matter was settled.

試験例1(水中溶出試験)
縦50cm、横40cmのホーロー製バットに水道水8リットルを入れ水深4cmとした。これに実施例1〜10、比較例1〜4の均一拡散性粒状農薬製剤を10アールあたり250g相当となるように施用処理した。処理1、3、7、21、35日後に採水し、HPLC分析により水中の成分濃度を水中溶出率として求めた。その結果を表1に示す。

Figure 0004919662
Test example 1 (water dissolution test)
8 liters of tap water was put into a 50 cm long and 40 cm wide enameled bat to a depth of 4 cm. The uniform diffusible granular agricultural chemical formulations of Examples 1 to 10 and Comparative Examples 1 to 4 were applied to this so as to correspond to 250 g per 10 ares. Water was collected after 1, 3, 7, 21, and 35 days of treatment, and the component concentration in water was determined as the dissolution rate in water by HPLC analysis. The results are shown in Table 1.
Figure 0004919662

表1より、実施例1〜7の均一拡散性粒状農薬製剤は、その農薬活性成分である除草剤のスルホニルウレア系化合物又はジフルオロメタンスルホニルアニリド誘導体又はその塩について、その水中溶出率が、処理1日後から35日後までの試験において、比較例1〜3に対して低く推移していることから、徐放化されていることが分る。  From Table 1, the uniform diffusible granular agricultural chemical preparations of Examples 1 to 7 have an elution rate in water of the herbicide sulfonylurea compound or difluoromethanesulfonylanilide derivative or salt thereof as an agricultural chemical active ingredient after 1 day of treatment. In the test from 35 to 35 days later, it can be seen that the release was slow compared to Comparative Examples 1 to 3.

また、実施例8と比較例4とを対比すると、後者は前者に対し水中濃度が低いまま推移し、農薬活性成分の溶出は初期のごく一部だけにとどまり、継続せず、従って均一拡散性粒状農薬製剤中の農薬活性成分の多くが未利用のまま残存している点で明らかに劣る。  Further, when Example 8 and Comparative Example 4 are compared, the latter has a lower concentration in water than the former, and the elution of the agrochemical active ingredient is only a small part of the initial stage and does not continue. It is clearly inferior in that many of the pesticidal active ingredients in the granular pesticide preparation remain unused.

また、実施例5と比較例3とを対比すると、後者は前者に対し水中濃度が高いまま推移し、塩基性物質が含有されていないことにより、農薬活性成分の徐放化が低下することが分る。  Moreover, when Example 5 and Comparative Example 3 are contrasted, the latter may remain at a higher concentration in water than the former, and the sustained release of the pesticidal active ingredient may be reduced due to the absence of basic substances. I understand.

試験例2(圃場拡散性)
図1に示す、短辺20m、長辺50m、水深5cmの水田圃場の風上2辺より、実施例5の均一拡散性粒状農薬製剤を手撒きで散布した。散布してから48時間後、図1に示す(A〜L)地点より水を採取して分析し、理論上農薬活性成分が均一に水に分散した場合の水中濃度を100%としたときの比率を求め、さらに各地点の水中濃度の標準偏差を平均で除し変動率を算出した。その結果を表2に示す。

Figure 0004919662
Test example 2 (field diffusibility)
The uniform diffusible granular agrochemical formulation of Example 5 was spread by hand from the upwind two sides of a paddy field having a short side of 20 m, a long side of 50 m, and a water depth of 5 cm shown in FIG. 48 hours after spraying, water is collected from the points (A to L) shown in FIG. 1 and analyzed. When the concentration of the agrochemical active ingredient is theoretically dispersed in water, the water concentration is 100%. The ratio was calculated, and the standard deviation of the water concentration at each point was divided by the average to calculate the fluctuation rate. The results are shown in Table 2.
Figure 0004919662

表2より、この均一拡散性粒状農薬製剤を施用した場合、農薬活性成分の水中均一性は良好であることが分る。  From Table 2, it can be seen that when this uniform diffusible granular agricultural chemical formulation is applied, the uniformity of the agricultural chemical active ingredient in water is good.

本発明の均一拡散性粒状農薬製剤は、簡便な方法で調製することができ、且つ農薬活性成分の溶出を適度に徐放化させ、それにより長期にわたり農薬活性成分の薬効を発揮させるとともに、環境中への農薬活性成分の放出低減により環境負荷を低減させ、農薬活性成分により引き起こされる薬害、例えば対象作物に対する薬害等を軽減又は防止しうる粒状農薬製剤を、簡便な散布法により水田全体に均一に拡散させることを可能にし、農作業の省力化に資するという顕著な効果を奏する。  The uniform diffusible granular agricultural chemical formulation of the present invention can be prepared by a simple method, and the elution of the agricultural chemical active ingredient is moderately and gradually released, thereby exhibiting the medicinal effect of the agricultural chemical active ingredient over a long period of time, and the environment. Reduce the environmental burden by reducing the release of active agricultural chemicals to the inside, and reduce or prevent phytotoxicity caused by pesticidal active ingredients, such as phytotoxicity on target crops, etc. This makes it possible to spread the water and contributes to labor saving in agricultural work.

Claims (4)

酸性農薬活性成分とカチオン界面活性剤と塩基性物質とを含有する30分以内には水中で崩壊しない非崩壊型農薬粒状物、界面活性剤及び浮遊性成分を含有し、粒径3mm以上の粒子の質量割合が80質量%以上である粒度分布と水面に投下した直後には水面に浮遊する性質を有するが、30分以内に水面で崩壊する均一拡散性粒状農薬製剤であって、
前記酸性農薬活性成分がベンスルフロンメチル及びピラゾスルフロンエチルから選ばれるスルホニルウレア系除草剤または一般式
Figure 0004919662
(式中のR は水素原子、アルキル基又はアルコキシアルキル基である)
で表されるジフルオロメタンスルホニルアニリド誘導体又はその塩であり、
前記カチオン界面活性剤が、ジ(C 〜C 22 アルキル)ジメチルアンモニウムクロライドであって、水中でゲル化するか、あるいは膨潤性を示すものであり、かつ、
前記塩基性物質が炭酸水素ナトリウム、炭酸ナトリウム、水酸化カルシウム、炭酸カルシウム、塩基性ホワイトカーボン及び塩基性の酸性白土からなる群から選ばれる一種以上であることを特徴とする均一拡散性粒状農薬製剤。
Non-disintegrating pesticide particulates that do not disintegrate in water within 30 minutes, containing an acidic pesticide active ingredient, a cationic surfactant, and a basic substance, a particle containing a surfactant and a floating component, and having a particle size of 3 mm or more immediately after the weight ratio of was dropped on the particle size distribution and water is 80 mass% or more have the property of floating on the water surface, a uniform diffusing granular pesticide formulation you disintegrate in water within 30 minutes,
A sulfonylurea herbicide or a general formula wherein the acidic agrochemical active ingredient is selected from bensulfuron methyl and pyrazosulfuron ethyl
Figure 0004919662
(Wherein R 1 is a hydrogen atom, an alkyl group or an alkoxyalkyl group)
A difluoromethanesulfonylanilide derivative represented by
The cationic surfactant is di (C 8 -C 22 alkyl) dimethylammonium chloride, which gels in water or exhibits swelling properties; and
Uniformly diffusible granular agricultural chemical formulation, wherein the basic substance is at least one selected from the group consisting of sodium hydrogen carbonate, sodium carbonate, calcium hydroxide, calcium carbonate, basic white carbon and basic acidic clay. .
浮遊性成分が、無機中空体又はプラスチック中空体である請求項1記載の均一拡散性粒状農薬製剤。  The uniform diffusible granular agricultural chemical preparation according to claim 1, wherein the floating component is an inorganic hollow body or a plastic hollow body. 請求項1又は2記載の均一拡散性粒状農薬製剤を製造するにあたり、前記非崩壊型農薬粒状物を、前記界面活性剤及び前記浮遊性成分とともに造粒処理に付し、粒径1〜20mmの球状あるいは短径1〜20mm、長径3〜40mmの横長の形状とする均一拡散性粒状農薬製剤の製造方法であって、
前記造粒処理を、前記非崩壊型農薬粒状物の粒径又は粒長よりも大きな目開き径のスクリーンより押出し造粒することにより行うことを特徴とする均一拡散性粒状農薬製剤の製造方法。
In producing a homogeneous diffusing granular pesticide formulation according to claim 1 or 2, wherein said non-disintegrable pesticide granules, subjected to granulation treatment with the surfactant and the floating component, particle size 1~20mm A method for producing a uniform diffusible granular agrochemical formulation in a spherical shape or a horizontally long shape with a minor axis of 1-20 mm and a major axis of 3-40 mm ,
A method for producing a uniform diffusible granular agrochemical formulation , wherein the granulation treatment is performed by extrusion granulation from a screen having an opening diameter larger than the particle size or grain length of the non-disintegrating agrochemical granular material .
請求項1又は2記載の均一拡散性粒状農薬製剤を製造するにあたり、前記非崩壊型農薬粒状物と、農薬活性成分とを前記界面活性剤及び前記浮遊性成分とともに造粒処理に付し、粒径1〜20mmの球状あるいは短径1〜20mm、長径3〜40mmの横長の形状とする均一拡散性粒状農薬製剤の製造方法であって、
前記造粒処理を、前記非崩壊型農薬粒状物の粒径又は粒長よりも大きな目開き径のスクリーンより押出し造粒することにより行うことを特徴とする均一拡散性粒状農薬製剤の製造方法。
In producing a homogeneous diffusing granular pesticide formulation according to claim 1 or 2, wherein said non-disintegrable pesticide granules, subjected to the pesticidal active ingredient in the granulation process with the surfactant and the floating component, grain A method for producing a uniform diffusible granular pesticide preparation having a spherical shape with a diameter of 1 to 20 mm or a horizontally long shape with a minor axis of 1 to 20 mm and a major axis of 3 to 40 mm ,
A method for producing a uniform diffusible granular agrochemical formulation , wherein the granulation treatment is performed by extrusion granulation from a screen having an opening diameter larger than the particle size or grain length of the non-disintegrating agrochemical granular material .
JP2005514188A 2003-09-26 2004-09-22 Uniform diffusible granular pesticide formulation Expired - Lifetime JP4919662B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005514188A JP4919662B2 (en) 2003-09-26 2004-09-22 Uniform diffusible granular pesticide formulation

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2003336540 2003-09-26
JP2003336540 2003-09-26
JP2005514188A JP4919662B2 (en) 2003-09-26 2004-09-22 Uniform diffusible granular pesticide formulation
PCT/JP2004/013776 WO2005029956A1 (en) 2003-09-26 2004-09-22 Uniformly diffusible granular pesticide composition

Publications (2)

Publication Number Publication Date
JPWO2005029956A1 JPWO2005029956A1 (en) 2007-11-15
JP4919662B2 true JP4919662B2 (en) 2012-04-18

Family

ID=34386097

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2005514188A Expired - Lifetime JP4919662B2 (en) 2003-09-26 2004-09-22 Uniform diffusible granular pesticide formulation

Country Status (4)

Country Link
JP (1) JP4919662B2 (en)
KR (1) KR101130428B1 (en)
CN (1) CN1856247B (en)
WO (1) WO2005029956A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012077961A2 (en) * 2010-12-06 2012-06-14 신젠타 파티서페이션즈 아게 Floating diffusible pesticide tablet formulation
US20130053247A1 (en) * 2011-08-25 2013-02-28 Dow Agrosciences Llc Increasing particle size of pesticides to reduce movement in soil
JP2013082632A (en) 2011-10-05 2013-05-09 Bayer Cropscience Ag Agrochemical formulation and manufacturing method of the same
CN104782620B (en) * 2013-02-22 2018-04-27 住友化学株式会社 Waterbourne granular insecticide, and the packed agrochemical formulations containing it
KR102296447B1 (en) * 2014-04-18 2021-08-31 구미아이 가가쿠 고교 가부시키가이샤 Large granular agrochmical composition that floats on water surface and production method therefor
EP3238540A1 (en) * 2016-04-28 2017-11-01 Bayer CropScience Aktiengesellschaft Timed-release-type granular agrochemical composition and method for manufacturing same
CN115191436B (en) * 2022-09-19 2022-11-22 山东省寿光蔬菜产业集团有限公司 Pest attractant composition and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6322502A (en) * 1986-07-14 1988-01-30 Kao Corp Production of granular agricultural chemical
JP2002179507A (en) * 2000-10-05 2002-06-26 Kumiai Chem Ind Co Ltd Uniformly dispersible granular agrochemical preparation and method for spraying the same preparation
WO2003082008A1 (en) * 2002-03-29 2003-10-09 Kumiai Chemical Industry Co., Ltd. Granular agricultural-chemical composition

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0466509A (en) * 1990-06-29 1992-03-02 Nissan Chem Ind Ltd Granular herbicide for paddy field
ATE150254T1 (en) * 1991-01-24 1997-04-15 Monsanto Co FORMULATIONS OF GLYPHOSATES
JP3180359B2 (en) * 1991-02-28 2001-06-25 日本曹達株式会社 Method for producing tablet-like effervescent pesticidal composition
JPH05155715A (en) * 1991-12-04 1993-06-22 Sumitomo Chem Co Ltd Agricultural chemical preparation
JP3522784B2 (en) * 1993-03-11 2004-04-26 バイエルクロップサイエンス株式会社 Pesticide granules
JP2931869B2 (en) * 1994-11-17 1999-08-09 北興化学工業株式会社 Granular pesticide wettable powder
JPH10109903A (en) * 1996-10-04 1998-04-28 Sankyo Co Ltd Granular herbicide for rice paddies
JP3781487B2 (en) * 1996-10-04 2006-05-31 三共アグロ株式会社 Herbicide for paddy field
JP4302232B2 (en) * 1999-04-23 2009-07-22 クミアイ化学工業株式会社 Water-floating granular agrochemical formulation, method for producing the same and method for spraying the same
JP2000319103A (en) * 1999-05-13 2000-11-21 Kumiai Chem Ind Co Ltd Granular agrochemical preparation floatable on water surface and its production
JP3900237B2 (en) * 2000-04-14 2007-04-04 財団法人理工学振興会 Method for adjusting vaporization rate of aromatic compound using crystallization with surfactant
JP4824215B2 (en) * 2001-07-24 2011-11-30 クミアイ化学工業株式会社 Dispersion method of granular agricultural chemical composition and granular agricultural chemical mixture
JP4443101B2 (en) * 2002-03-22 2010-03-31 バイエルクロップサイエンス株式会社 Improved agrochemical composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6322502A (en) * 1986-07-14 1988-01-30 Kao Corp Production of granular agricultural chemical
JP2002179507A (en) * 2000-10-05 2002-06-26 Kumiai Chem Ind Co Ltd Uniformly dispersible granular agrochemical preparation and method for spraying the same preparation
WO2003082008A1 (en) * 2002-03-29 2003-10-09 Kumiai Chemical Industry Co., Ltd. Granular agricultural-chemical composition

Also Published As

Publication number Publication date
CN1856247A (en) 2006-11-01
CN1856247B (en) 2010-05-05
KR20060063914A (en) 2006-06-12
KR101130428B1 (en) 2012-03-27
JPWO2005029956A1 (en) 2007-11-15
WO2005029956A1 (en) 2005-04-07

Similar Documents

Publication Publication Date Title
US7638506B2 (en) Granular agrochemical composition
JP3871230B2 (en) Pesticide granular composition and spraying method
JP4919662B2 (en) Uniform diffusible granular pesticide formulation
JP4919663B2 (en) Granular pesticide formulation
JPH10109905A (en) Granular herbicide composition for rice paddies and its scattering method
JP4302232B2 (en) Water-floating granular agrochemical formulation, method for producing the same and method for spraying the same
JP5285074B2 (en) Granule wettable powder
JPH10245303A (en) Production of granular agrochemical formulation
JP2001240502A (en) Agrochemical composition for rice field, its manufacturing method and method for scattering the same
JP4897132B2 (en) Agrochemical granular composition with good disintegration
JP2000319103A (en) Granular agrochemical preparation floatable on water surface and its production
JP4617530B2 (en) Solid agrochemical composition
JP4410322B2 (en) Anhydrous sodium sulfate-containing granular composition and process for producing the same
JP4421309B2 (en) Agricultural and horticultural granule wettable powder
JP2002029903A (en) Elution-controlled agrochemical granule and method for producing the same
JP4526593B2 (en) Anhydrous sodium sulfate-containing granular composition and process for producing the same
JP2000319102A (en) Agrochemical preparation of type to be cast on water surface
JP2002226304A (en) Method for producing sustained release type fine grain
JP2002128602A (en) Agrochemical composition for paddy field

Legal Events

Date Code Title Description
RD01 Notification of change of attorney

Free format text: JAPANESE INTERMEDIATE CODE: A7421

Effective date: 20090608

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20110415

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20110614

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20120127

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20120131

R150 Certificate of patent or registration of utility model

Free format text: JAPANESE INTERMEDIATE CODE: R150

Ref document number: 4919662

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20150210

Year of fee payment: 3

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250