Nothing Special   »   [go: up one dir, main page]

JP3746831B2 - Aqueous pesticide formulation - Google Patents

Aqueous pesticide formulation Download PDF

Info

Publication number
JP3746831B2
JP3746831B2 JP08373496A JP8373496A JP3746831B2 JP 3746831 B2 JP3746831 B2 JP 3746831B2 JP 08373496 A JP08373496 A JP 08373496A JP 8373496 A JP8373496 A JP 8373496A JP 3746831 B2 JP3746831 B2 JP 3746831B2
Authority
JP
Japan
Prior art keywords
water
parts
suspended
sol
viscosity
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 - Fee Related
Application number
JP08373496A
Other languages
Japanese (ja)
Other versions
JPH09278602A (en
Inventor
隆志 廣川
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.)
Nippon Soda Co Ltd
Original Assignee
Nippon Soda 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 Nippon Soda Co Ltd filed Critical Nippon Soda Co Ltd
Priority to JP08373496A priority Critical patent/JP3746831B2/en
Publication of JPH09278602A publication Critical patent/JPH09278602A/en
Application granted granted Critical
Publication of JP3746831B2 publication Critical patent/JP3746831B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Landscapes

  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

【0001】
【発明の属する技術分野】
本発明は、水に難溶性の農薬原体を有効成分とし、低粘度で、且つ長期にわたって安定な性状を保持する水懸濁状農薬製剤に関する。
【0002】
【従来の技術】
従来、水難溶性の農薬原体は、液剤化又は乳剤化が困難であることから、粉剤、水和剤等の製剤形態で使用されてきた。しかし粉剤は散布に際して周囲への飛散が多く、水和剤は水に希釈する際に粉立つという、使用者に対する安全衛生面で好ましくない面を有していた。
【0003】
このため、近年微粒子化された農薬原体を水等に分散懸濁化した水懸濁状農薬製剤、即ちゾル剤又はフロアブル剤と呼ばれる液状の製剤品(以下、これらをゾル剤と称する場合がある。)が多く用いられるようになってきた。ゾル剤は、水和剤と同様に水に希釈して、又は原液の状態で散布されるため、水希釈時の粉立ちがないこと、計量が水和剤に比べて容易であることなど優れた製剤形態であり、種々の組成が検討されてきた。
【0004】
例えば、(a)水難溶性の農薬活性成分に水、溶剤、界面活性剤及びカルボキシメチルセルロース等の水溶性高分子を加えて水中に懸濁化した製剤(特公昭58−24401号公報)、(b)ヘテロポリサッカライドガムを加えて水中に懸濁化した製剤(特開昭49−133531号公報)、(c)ノニオン界面活性剤とヘテロ多糖類ガムを加えて水中に懸濁化した製剤(特開昭52−128226号公報)、(d)界面活性剤及びコロイド状含水ケイ酸アルミニウムを加えて水中に懸濁化した製剤(特公昭54−11368号公報)、
【0005】
(e)ヘテロポリサッカライドガムと酸化アルミニウムを加えて水中に懸濁化した製剤(特開平1−268604号公報)、(f)ベントナイト鉱物質とヘテロポリサッカライドガムを加えて水中に懸濁した製剤(特公平7−86081号公報)、(g)ベントナイト鉱物質とコロイド性酸化ケイ素を加えて水中に懸濁化した製剤(特公平7−116001号公報)等が知られている。
【0006】
しかしながら、従来の(a)〜(e)のゾル剤は、ゾル剤に要求される物理性状の諸条件を満たすことは困難であり、製剤品の保存安定性を良好にし、懸濁均一性を長期にわたって保持させるためには、高い粘性が必要であり、そのため保存容器への充填が容易ではなく、容器から製剤品を取りだした際の容器内残量が多くなり、また容器内残量の確認が容易でないとともに、計量が不正確となり、空中散布時等における原液散布に支障が生じる。
【0007】
一方、実用上問題がなくなるまで粘性を低下させると、保存安定性が悪くなり、沈降した粒子はやがて再分散不可能なハードケーキング層を形成するなどの問題点がある。また(f)及び(g)のゾル剤についても、ベントナイト鉱物質の経時的増粘性等を改善するため、ヘテロポリサッカライドガム又はコロイド性酸化ケイ素を併用し、保存安定性を改善しているが、実質的な低粘度領域、即ち、100mPa.s以下の粘度では、長期において粘度変化等の物理性状を安定に保ち、かつ保存安定性の良好なゾル剤を得ることは困難であった。
【0008】
【発明が解決しようとする課題】
本発明が解決しようとする課題は、水中での分散性がよく、粘性が低く、長期間保存しても沈降分離を殆ど生ぜず、長期にわたり良好な粘度特性及び保存安定性を有する、水難溶性農薬原体を含む水懸濁状農薬製剤を提供することにある。
【0009】
【課題を解決するための手段】
本発明者等は、これらの課題を解決するため種々研究した結果、100mPa.s以下の低粘度領域においてさえ粘度変化等の物理性状を安定に保ち、且つ実用上問題のない保存安定性を示す水懸濁状農薬製剤を見い出し、本発明を完成するに至った。
【0010】
即ち、本発明は、1種又は2種以上の水難溶性農薬原体と、ホモポリサッカライドと、スメクタイト系粘土鉱物質とを含有することを特徴とする水懸濁状農薬製剤である。また、本発明は、該水懸濁状農薬製剤に更にヘテロポリサッカライドガムを併用することを特徴とする水懸濁状農薬製剤や、カルボキシメチルセルロースを併用することを特徴とする水懸濁状農薬製剤を含むものである。
【0011】
また本発明の水懸濁状農薬製剤は、用いるホモポリサッカライドが特にプルランであることを特徴とする水懸濁状農薬製剤や、水懸濁状農薬製剤の粘度が室温で10〜200mPa.sであることを特徴とする水懸濁状農薬製剤をも含むものである。
【0012】
【発明の実施の形態】
本発明に使用可能な水難溶性農薬原体は、水に難溶性であれば特に制限はなく、その配合量は、本水懸濁状農薬製剤中、通常1〜60重量%が好ましい。このような農薬原体としては、例えば、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)、5−(2,4−ジクロロフェノキシ)−2−ニトロメチルベンゾアート(ビフェノックス)、2−ブロモ−N−(α,α−ジメチルベンジル)−3,3−ジメチルブタナミド(ブロモブチド)、[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)、
【0013】
[メチル−α−(4,6−ジメトキシピリミジン−2−イル)カルバモイルスルファモイル]−O−トルアート(ベンスルフロンメチル)、1−(2−クロロイミダゾ[1,2−a]ピリジン−3−イルスルホニル)−3−(4,6−ジメトキシピリジン−2−イル)尿素(イマゾスルフロン)、1−(α,α−ジメチルベンジル)−3−(パラトリル)尿素(ダイムロン)、1−{[O−(シクロプロピルカルボニル)フェニル]スルファモイル}−3(4,6−ジメトキシ−2−ピリミジニル)−尿素(AC 322,140)等の除草剤;
【0014】
2−メチル−3’−イソプロポキシベンズアニリド(メプロニル)、4,5,6,7−テトラクロロイソフタロニトリル(TPN)、マンガニーズエチレンビス(ジチオカルバマート)(マンネブ)、ジメチル−4,4’−O−フェニレンビス(3−チオアロファナート)(チオファネートメチル)、8−オキシキノリン銅、水酸化第二銅、硫黄等の殺菌剤;ジメチル−2−クロロ−1−(2,4−ジクロロフェニル)ビニルホスファート(ジメチルビンホス)、1−ナフチルカルバマート(NAC)、m−トリルメチルカルバマート(MTMC)、
【0015】
3,4−キシリルメチルカルバマート(MPMC)、0,S−ジメチル−N−アセチルホスホロアミドチオアート(アセフェート)、2−sec−ブチル−4,6−ジニトロフェニル−3−メチルクロトナート(ビナパクリル)、トリシクロヘキシルチンヒドロオキシド(プリクトラン)、S−4−フェノキシブチル−N,N−ジメチルチオカルバマート(フェノチオカルブ)、
【0016】
2−sec−ブチルフェニル−N−メチルカルバマート(BPMC)、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)等の殺虫剤又は殺ダニ剤等が挙げられる。本発明の水懸濁状農薬製剤には、これらの農薬原体を1種以上用いることができ、除草剤、殺菌剤、殺虫剤等を複数種混合することも可能である。
【0017】
本発明で使用されるホモポリサッカライドは、1種の単糖より構成される多糖類を表わし、例えばプルラン、カードラン等が挙げられる。プルランは、微生物の発酵作用により生産される直鎖状高分子量の多糖類で、構成単糖類はグルコースからなる。
【0018】
本発明で使用されるスメクタイト系粘土鉱物質には、天然及び合成のスメクタイト粘土鉱物が含まれる。スメクタイトとは、通常葉ろう石及び滑石の粘土構造において、種々の金属原子の置換によって得られる膨張性粘土鉱物の一群を示し、例えばモンモリロナイト、サポナイト、ヘクトライト、ベントナイト、ベイデライト、ノントロナイト、サウコライト、ステペンサイト等を例示することができ、好ましくはモンモリロナイト、ベントナイトが良い。
【0019】
これらのスメクタイト系粘土鉱物質は、例えば、ビーガムT、ビーガムB、バンゲルB(バンダービルド社製、登録商標)、ラポナイトB、ラポナイトRD、ラポナイトS(日本シリカ工業株式会社製、登録商標)、クニゲルVA、クニゲルV1、クニピアF(クニミネ工業株式会社製、登録商標)、サンベントナイトKA−1、サンベントナイトKG−1(サンベントナイト工業株式会社製、登録商標)、オスモスN(白石工業株式会社製、登録商標)等の商品名で市販されている。
【0020】
本発明で使用されるホモポリサッカライド及びスメクタイト系粘土鉱物質の配合量は、本剤中、通常それぞれ0.5〜3重量%程度であり、製剤品の粘度が10〜200mPa.sとなるようにそれぞれの配合量を調整すれば良い。
更に、ホモポリサッカライド及びスメクタイト系粘土鉱物質の配合比は、重量比で、スメクタイト系粘土鉱物質1に対し、ホモポリサッカライド0.5〜5の範囲において使用するのが好ましく、特に好ましくは1〜3である。
【0021】
本発明の水ゾル剤は、上述の農薬原体、ホモポリサッカライド及びスメクタイト系粘土鉱物質を水性溶媒に懸濁又は一部溶解させたものである。水性溶媒としては、水又は水に他の有機溶媒を加えたものが使用される。水性溶媒の配合量は、本ゾル剤中、30〜95重量%である。
【0022】
本発明の水懸濁状農薬製剤は、上記組成に更にヘテロポリサッカライドガム及び/又はカルボキシメチルセルロースを併用することにより、その保存安定性が更に改善される。本発明に使用されるヘテロポリサッカライドガムとは、2種以上の単糖より構成される多糖類を表し、例えばキサンタンガム、ウエランガム、グアーガム、ローカストビーンガム、ラムザンガム等が挙げられる。
【0023】
キサンタンガムとは、微生物の発酵作用により生産される直鎖状高分子量の多糖類で、分子量は約200万、構成単糖類はグルコース、マンノース、グルクロン酸からなる。
【0024】
本発明に使用されるカルボキシメチルセルロースとは、カルボキシメチル基を含有するホモポリサッカライド誘導体で、構成する無水グルコースのカルボキシメチル基の置換度が0.6〜1.5の範囲のものが好ましい。本発明で使用されるヘテロポリサッカライドガム及びカルボキシメチルセルロースの配合量は、本ゾル剤中、通常それぞれ0.01〜3重量%程度であり、好ましくは0.05〜1重量%である。
【0025】
また本発明の水懸濁状農薬製剤には、界面活性剤を併用しても良い。用いられる界面活性剤としては、公知慣用のノニオン界面活性剤、アニオン界面活性剤がいずれも制限なく使用できる。
【0026】
ノニオン界面活性剤の具体例としては、ポリオキシエチレンアリールフェニルエーテル、ポリオキシエチレンアルキルアリールエーテル、ショ糖脂肪酸エステル、ポリグリセリン脂肪酸エステル、ポリオキシエチレンソルビタンアルキラート、ポリオキシエチレンアルキルエステル、ポリオキシエチレンアルキルエーテル等を挙げることができる。
【0027】
アニオン界面活性剤の具体例としては、リグニンスルホン酸塩、アルキルアリールスルホン酸塩、ポリオキシエチレンアリールフェニルエーテルリン酸エステル化塩、ポリオキシエチレンアリールフェニルエーテル硫酸エステル化塩、ポリオキシエチレンアルキルフェニルエーテルリン酸エステル化塩、ジオクチルスルホコハク酸塩、ポリカルボン酸塩等を挙げることができる。
【0028】
これらの界面活性剤は単独で使用しても、異種又は同種の界面活性剤の2種以上を任意の割合で併用してもよい。特にノニオン界面活性剤とアニオン界面活性剤を併用して用いるのが懸濁安定性及び水中での分散性の点から好ましい。その配合量は、通常、水懸濁状農薬製剤の1〜10重量%が良い。
【0029】
本発明においては、本発明の効果を阻害しない範囲で、上述のホモポリサッカライド、スメクタイト系粘土鉱物質、ヘテロポリサッカライドガム及びメチルセルロース以外の、通常使用される公知慣用の増粘剤を添加し得る。該増粘剤としては、メチルセルロース、ヒドロキシエチルセルロース、ポリビニルピロリドン、酸化ケイ素、酸化アルミニウム等が挙げられる。
【0030】
本発明の水懸濁状農薬製剤は、上記成分以外に、更に必要に応じて消泡剤、凍結防止剤等の添加剤を含んでもよい。消泡剤としては、例えばシリコン系のものが、また凍結防止剤としては、例えばエチレングリコール、ジエチレングリコール等のジオール類や、グリコールエーテル類、尿素等が好適に使用される。
【0031】
本発明の水懸濁状農薬製剤は、取扱い及び使用を容易にするために、粘度は20℃において10〜200mPa.sとするのが良く、この範囲の粘度であれば、製剤品を取り出した際の容器内残量が少なく薬剤を無駄なく使用することができ、正確な計量が可能となり、また水中での分散性に優れると共に、空中散布時等における原液散布の際ノズル部分の通過性が良くて、一定量の薬剤散布が可能となるような低粘度な製剤にすることができる。
【0032】
尚、ここで言う粘度は、B型回転粘度計(BM型、東京計器株式会社製)を用いて、ローターNo.3、ローター回転数60rpm、製剤品温度20±0.4℃の測定条件での測定粘度である。
【0033】
水懸濁製剤にホモポリサッカライドを単独で使用した場合には、保存安定性の良好な製剤は得られず、またスメクタイト系粘土鉱物質を単独で使用した場合には、経時的に粘性が高くなり、好ましい結果は得られない。また、スメクタイト系粘土鉱物質とカルボキシメチルセルロースの併用では、経時的に粘性が高くなり、これに伴い水分散性が悪くなる。
【0034】
本発明ではホモポリサッカイドとスメクタイト系粘土鉱物質とを併用することにより、あるいは更にヘテロポリサッカライドガム及び/又はカルボキシルメチルセルロースを併用することにより保存安定性に優れ、粘性が低いという良好な物理性状が得られる。
【0035】
次に、本発明のゾル剤の製造法の概略を示す。
まず、ホモポリサッカライド及びスメクタイト系粘土鉱物質を所定量の水性溶媒に加え、撹拌機にて分散させた後、界面活性剤、農薬原体を加える。更に必要に応じて凍結防止剤、消泡剤等を加え、撹拌機により混合分散させる。
【0036】
次に、この混合物を湿式粉砕機、例えばダイノミルKDL型(WAB社製)、システムゼータLMZ型(アシザワ株式会社製)、パールミルTEX型(アシザワ株式会社製)等を用いて農薬原体の大部分が10μm以下、好ましくは0.1〜7μmの範囲の平均粒子径となるように湿式粉砕を行い、目的の水懸濁状農薬製剤(ゾル剤)を得る。
【0037】
農薬原体及び界面活性剤等の副原料を加える順序は、泡立ち等の工程上の都合により適宣変更しても良いが、ホモポリサッカライド及びスメクタイト系粘土鉱物質は、予め水性溶媒に十分分散又は溶解しておくことが好ましく、農薬原体については界面活性剤を分散又は溶解後に加えることが好ましい。
【0038】
【実施例】
以下、本発明を実施例により更に詳しく説明するが、本発明は当該実施例のみに限定されるものではない。尚、以下の「部」は「重量部」を表わす。
【0039】
[実施例1]
プルラン1部とクニピアF1部とを、水78.3部に混合分散させ、これにポリオキシエチレンアリールフェニルエーテル(竹本油脂株式会社製)0.6部及びポリオキシエチレンアリールフェニルエーテル硫酸エステル化塩(東邦化学工業株式会社製)1.0部を加えて混合溶解させた後、次にピリブチカルブ原体12部、変性シリコーンエマルジョン0.1部及びエチレングリコール6部を加え、湿式粉砕機にて粉砕し均質な水懸濁状農薬製剤(ゾル剤)を得た。
【0040】
[実施例2]
プルラン2部とクニピアF1部とを水77.1部に混合分散させ、これにショ糖脂肪酸エステル(竹本油脂株式会社製)0.8部、ポリオキシエチレンアリールフェニルエーテルリン酸エステル化塩(東邦化学工業株式会社製)1.0部及びポリカルボン酸塩1部を加えて混合溶解させた後、ピリブチカルブ原体12部、変性シリコーンエマルジョン0.1部及びエチレングリコール6部を加え、湿式粉砕機にて粉砕し均質なゾル剤を得た。
【0041】
[実施例3]
プルラン3部及びクニピアF1部を水76.1部に混合分散させ、これにポリオキシエチレン・ポリオキシプロピレントリスチリルフェニルエーテル(ローヌプーラン株式会社製)0.8部、ポリオキシエチレンノニルフェニルエーテルリン酸エステル化塩(松本油脂株式会社製)1.0部を加えて混合溶解させた後、ピリブチカルブ原体12部、変性シリコーンエマルジョン0.1部及びエチレングリコール6部を加え、湿式粉砕機にて粉砕し均質なゾル剤を得た。
【0042】
[実施例4]
プルラン2部、クニピアF1部及びキサンタンガム0.05部を水77.25部に混合分散させ、これに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(竹本油脂株式会社製)0.6部、ポリオキシエチレンアリールフェニルエーテルリン酸エステル化塩(同上)1.0部を加えて混合溶解させた後、ピリブチカルブ原体12部、変性シリコーンエマルジョン0.1部及びエチレングリコール6部を加え、湿式粉砕機にて粉砕し均質なゾル剤を得た。
【0043】
[実施例5]
プルラン2部、クニピアF1部及びカルボキシメチルセルロース0.1部を水77.2部に混合分散させ、これにポリオキシエチレンノニルフェニルエーテル(松本油脂株式会社製)0.6部、ポリオキシエチレンアリールフェニルエーテルリン酸エステル化塩(同上)1.0部を加えて混合溶解させた後、ピリブチカルブ原体12部、変性シリコーンエマルジョン0.1部及びエチレングリコール6部を加え、湿式粉砕機にて粉砕し均質なゾル剤を得た。
【0044】
[実施例6]
プルラン2部、クニピアF1部及びカルボキシメチルセルロース0.2部を水77.1部に混合分散させ、これにポリオキシエチレンアリールフェニルエーテル(ローヌプーラン株式会社製)0.6部、ポリオキシエチレンアリールフェニルエーテルリン酸エステル化塩(同上)1.0部を加えて混合溶解させた後、ピリブチカルブ原体12部、変性シリコーンエマルジョン0.1部及びエチレングリコール6部を加え、湿式粉砕機にて粉砕し均質なゾル剤を得た。
【0045】
[実施例7]
カードラン1.5部、クニピアF1部を水77.8部に混合分散させ、これに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モノオレアート(松本油脂株式会社製)0.6部、ポリオキシエチレンアリールフェニルエーテルリン酸エステル化塩(同上)1.0部を加えて混合溶解させた後、ピリブチカルブ原体12部、変性シリコーンエマルジョン0.1部及びエチレングリコール6部を加え、湿式粉砕機にて粉砕し均質なゾル剤を得た。
【0046】
[実施例8]
プルラン2部、クニピアF1部及びカルボキシメチルセルロース0.1部を水66.2部に混合分散させ、これにポリオキシエチレンアリールフェニルエーテル(同上)0.6部、ポリオキシエチレンアリールフェニルエーテル硫酸エステル化塩(同上)1.0部及びアルキルアリールスルホン酸ナトリウム共重合物1部を加えて混合溶解させた後、ピリブチカルブ原体10部、ビフェノックス1部、ブロモブチド12部、変性シリコーンエマルジョン0.1部及びエチレングリコール6部を加え、湿式粉砕機にて粉砕し均質なゾル剤を得た。
【0047】
[実施例9]
プルラン2部、クニピアF1部及びカルボキシメチルセルロース0.2部を水73.5部に混合分散させ、これにショ糖脂肪酸エステル(同上)0.8部、ポリオキシエチレンアリールフェニルエーテル硫酸エステル化塩(同上)1.0部を加えて混合溶解させた後、ピリブチカルブ原体10部、テニルクロール原体4部、ベンスルフロンメチル1.4部、変性シリコーンエマルジョン0.1部及びエチレングリコール6部を加え、湿式粉砕機にて粉砕し均質なゾル剤を得た。
【0048】
[比較例1]
実施例1のプルラン1部及びクニピアF1部を、プルラン3部に置き換えるとともに、水78.3部を77.3部に変えた以外は、実施例1と同様にしてピリブチカルブの均質なゾル剤を得た。
【0049】
[比較例2]
実施例1のプルラン1部及びクニピアF1部を、クニピアF1部に置き換えるとともに、水78.3部を79.3部に変えた以外は、実施例1と同様にしてピリブチカルブの均質なゾル剤を得た。
【0050】
[比較例3]
実施例1のプルラン1部及びクニピアF1部をクニピアF2部に置き換えた以外は、実施例1と同様にしてピリブチカルブの均質なゾル剤を得た。
【0051】
[比較例4]
実施例1のプルラン1部及びクニピアF1部をクニピアF3部に置き換えるとともに、水78.3部を77.3部に変えた以外は、実施例1と同様にしてピリブチカルブの均質なゾル剤を得た。
【0052】
[比較例5]
実施例1のプルラン1部及びクニピアF1部をキサンタンガム0.1部に置き換えるとともに、水78.3部を80.2部に変えた以外は、実施例1と同様にしてピリブチカルブの均質なゾル剤を得た。
【0053】
[比較例6]
実施例1のプルラン1部をキサンタンガム0.05部に置き換えるとともに、水78.3部を79.25部に変えた以外は、実施例1と同様にしてピリブチカルブの均質なゾル剤を得た。
【0054】
[比較例7]
実施例1のプルラン1部及びクニピアF1部をキサンタンガム0.05部及びクニピアF2部に置き換えるとともに、水78.3部を78.25部に変えた以外は、実施例1と同様にしてピリブチカルブの均質なゾル剤を得た。
【0055】
[比較例8]
実施例1のプルラン1部及びクニピアF1部をコロイド性酸化ケイ素1部及びクニピアF2部に置き換えるとともに、水78.3部を77.3部に変えた以外は、実施例1と同様にしてピリブチカルブの均質なゾル剤を得た。
【0056】
[比較例9]
実施例1のプルラン1部及びクニピアF1部をコロイド性酸化アルミニウム3部に置き換えるとともに、水78.3部を77.3部に変えた以外は、実施例1と同様にしてピリブチカルブの均質なゾル剤を得た。
【0057】
[比較例10]
実施例1のプルラン1部及びクニピアF1部をコロイド性酸化ケイ素3部に置き換えるとともに、水78.3部を77.3部に変えた以外は、実施例1と同様にしてピリブチカルブの均質なゾル剤を得た。
【0058】
[比較例11]
実施例1のプルラン1部及びクニピアF1部をカルボキシメチルセルロース0.3部に置き換えるとともに、水78.3部を80.0部に変えた以外は、実施例1と同様にしてピリブチカルブの均質なゾル剤を得た。
【0059】
次に、前記実施例1〜9及び比較例1〜11で調製したゾル剤について行った試験例1〜4を以下に示す。また各試験結果を表1及び表2に示す。表2中に付した*は凝集の発生を示す。表1及び表2に示す結果より、実施例のゾル剤は比較例のものより優れた保存安定性及び分散性を示し、粘度が低く、取扱性が良いことがわかる。
【0060】
(試験例1) 保存安定性の測定
調製したゾル剤を500mlのガラス瓶に入れ、40℃の恒温器に3カ月間静置保存し、ゾル剤の分離沈降性を測定した。測定は、液全体の高さに対する上澄液部の高さの割合(%)で算出した。また測定終了後、光学顕微鏡(×400)及び粒度分布測定装置(LS230:コールター社製)を用いて、凝集物の形成の有無を確認した。保存安定性は上澄液部の割合が小さいほど良好であり、また凝集物の形成はゾル剤として不適である。
【0061】
(試験例2) 粘度測定
試験例1で用いたゾル剤のガラス瓶の倒立を10回繰り返し行った後、粘度を測定した。測定にはB型粘度計(BM型、東京計器株式会社製)を用い、測定条件はローターNo.3、ローター回転数60rpm、製剤温度20±0.4℃で行った。粘度は経時的変化が少ないものほど良好である。
【0062】
(試験例3) 水中における分散性
250mlメスシリンダーに水250mlを入れ、ピペットにてゾル剤を滴下して分散状態を観察し、次の4段階での評価を行った。分散状態は良好なものほど好ましい。
【0063】
◎:分散状態が極めて良好。薬剤は水の中で拡散するように分散する。
○:分散状態が良好。薬剤は水の中で一部拡散しながら液滴の形で水中を落ちていくが、底に着くまでには分散してしまう。
△:分散状態がやや悪い。薬剤の大部分が液滴の形で底まで落ちるが、メスシリンダーを振れば分散する。
×:分散状態が悪い。薬剤は液滴の形で底まで落ち、メスシリンダーを振っても容易に分散しない。
【0064】
(試験例4) 容器残量の測定
ゾル剤100gを一般的な液状農薬保存用の100mlポリエチレン容器に入れ、容器残量の割合(%)を測定した。その方法はポリエチレン容器の倒立を10回繰り返し行った後、容器を10秒間倒立してゾル剤を取り出し、ポリエチレン容器の自重を引いた容器残量からその割合を算出した。容器残量は少ないほど好ましい。
【0065】
【表1】

Figure 0003746831
【0066】
【表2】
Figure 0003746831
【0067】
【発明の効果】
本発明は、▲1▼長期間保存しても沈降分離を殆ど生じることがなく、ハードケーキング及び凝集物を形成することがない。▲2▼粘性が低く、使用時の湿式粉砕効率が向上することにより生産性が向上し、保存容器への充填包装が容易である。
更に、使用時の正確に計量できることにより、安定した防除効果が得られることや、容器中の薬液残量の確認が容易であること、水中での分散性がよく、散布液調製が容易に行えること、また空中又は直播き散布における原液散布において散布装置内の目づまり等がなく、安定した薬剤散布が可能であること、使用後、容器中の薬液残量が少ないこと等の効果に加え、▲3▼低粘度領域、即ち100mPa.s以下の粘度においても、長期にわたって良好な粘度特性及び保存安定性を有する、優れた水懸濁状農薬製剤を提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a water-suspended agricultural chemical formulation that contains a pesticide raw material that is sparingly soluble in water as an active ingredient, has a low viscosity, and maintains stable properties over a long period of time.
[0002]
[Prior art]
Conventionally, poorly water-soluble pesticide bases have been used in the form of preparations such as powders and wettable powders because they are difficult to form into a solution or emulsion. However, the powder has a lot of scattering to the surroundings when sprayed, and the wettable powder has a undesirable aspect in terms of safety and hygiene for the user.
[0003]
For this reason, in recent years water-suspended agricultural chemical preparations in which finely divided agricultural chemical active ingredients are dispersed and suspended in water or the like, that is, liquid preparations called sols or flowables (hereinafter sometimes referred to as sols). Is often used. The sol is diluted with water or sprayed in the form of a stock solution like the wettable powder, so there is no powdering when diluted with water, and the weighing is easier than the wettable powder. Various formulations have been studied.
[0004]
For example, (a) a preparation obtained by adding water, a solvent, a surfactant, and a water-soluble polymer such as carboxymethylcellulose to a poorly water-soluble agricultural chemical active ingredient and suspending in water (Japanese Patent Publication No. 58-24401), (b ) Formulation in which heteropolysaccharide gum is added and suspended in water (Japanese Patent Laid-Open No. 49-133531), (c) Formulation in which nonionic surfactant and heteropolysaccharide gum are added and suspended in water (Sho 52-128226), (d) a preparation added with a surfactant and colloidal hydrous aluminum silicate and suspended in water (Japanese Patent Publication SHO 54-11368),
[0005]
(E) Formulation in which heteropolysaccharide gum and aluminum oxide are added and suspended in water (Japanese Patent Laid-Open No. 1-268604), (f) Formulation in which bentonite mineral and heteropolysaccharide gum are added and suspended in water (special No. 7-86081), (g) a preparation in which bentonite mineral and colloidal silicon oxide are added and suspended in water (Japanese Patent Publication No. 7-11001) are known.
[0006]
However, the conventional sols of (a) to (e) are difficult to satisfy the physical properties required for the sols, improve the storage stability of the drug product, and improve the suspension uniformity. In order to hold it for a long period of time, high viscosity is required, so filling into the storage container is not easy, the remaining amount in the container increases when the drug product is taken out from the container, and confirmation of the remaining amount in the container Is not easy, and the weighing becomes inaccurate, which hinders the spraying of the stock solution when spraying in the air.
[0007]
On the other hand, if the viscosity is lowered until there is no practical problem, the storage stability deteriorates, and the settled particles eventually form a hard caking layer that cannot be redispersed. In addition, the sols of (f) and (g) are also used in combination with heteropolysaccharide gum or colloidal silicon oxide in order to improve the time-dependent thickening of bentonite minerals. Substantially low viscosity region, ie 100 mPa.s. When the viscosity is s or less, it has been difficult to obtain a sol having a stable physical property such as a change in viscosity over a long period of time and having good storage stability.
[0008]
[Problems to be solved by the invention]
The problems to be solved by the present invention are poorly water-soluble, having good dispersibility in water, low viscosity, little sedimentation separation even after long-term storage, and good viscosity characteristics and storage stability over a long period of time. An object is to provide a water-suspended pesticide preparation containing an agrochemical base.
[0009]
[Means for Solving the Problems]
As a result of various studies to solve these problems, the present inventors have found that 100 mPa.s. The present inventors have completed the present invention by finding a water-suspended agrochemical formulation that maintains stable physical properties such as viscosity change even in a low viscosity region of s or less and exhibits storage stability without any practical problems.
[0010]
That is, the present invention is a water-suspended pesticide preparation characterized by containing one or two or more poorly water-soluble pesticide raw materials, a homopolysaccharide, and a smectite clay mineral substance. Further, the present invention provides a water-suspended agricultural chemical formulation characterized by further using a heteropolysaccharide gum in combination with the water-suspended agricultural chemical formulation, and a water-suspended agricultural chemical formulation characterized by using carboxymethylcellulose in combination. Is included.
[0011]
In addition, the water-suspended agricultural chemical formulation of the present invention is characterized in that the homopolysaccharide used is particularly pullulan, and the viscosity of the water-suspended agricultural chemical formulation is 10-200 mPa.s at room temperature. It also contains a water-suspended agricultural chemical formulation characterized by the above.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The poorly water-soluble pesticide raw material that can be used in the present invention is not particularly limited as long as it is poorly soluble in water, and the blending amount is usually preferably 1 to 60% by weight in the water-suspended pesticide preparation. Examples of such a pesticide raw material include O-3-tert-butylphenyl-6-methoxy-2-pyridyl (methyl) thiocarbamate (pyributycarb), 5- (2,4-dichlorophenoxy) -2- Nitromethylbenzoate (biphenox), 2-bromo-N- (α, α-dimethylbenzyl) -3,3-dimethylbutanamide (bromobutide), [2-chloro-N- (3-methoxy-2-thenyl) -2 ', 6'-dimethylacetanilide] (tenyl chlor),
[0013]
[Methyl-α- (4,6-dimethoxypyrimidin-2-yl) carbamoylsulfamoyl] -O-toluate (bensulfuronmethyl), 1- (2-chloroimidazo [1,2-a] pyridine-3- Ylsulfonyl) -3- (4,6-dimethoxypyridin-2-yl) urea (imazosulfuron), 1- (α, α-dimethylbenzyl) -3- (paratolyl) urea (Dimron), 1-{[O— Herbicides such as (cyclopropylcarbonyl) phenyl] sulfamoyl} -3 (4,6-dimethoxy-2-pyrimidinyl) -urea (AC 322,140);
[0014]
2-methyl-3'-isopropoxybenzanilide (mepronil), 4,5,6,7-tetrachloroisophthalonitrile (TPN), manganese ethylenebis (dithiocarbamate) (manneb), dimethyl-4,4 Bactericides such as' -O-phenylenebis (3-thioallophanate) (thiophanate methyl), 8-oxyquinoline copper, cupric hydroxide, sulfur; dimethyl-2-chloro-1- (2,4-dichlorophenyl ) Vinyl phosphate (dimethylvinphos), 1-naphthylcarbamate (NAC), m-tolylmethylcarbamate (MTMC),
[0015]
3,4-xylylmethylcarbamate (MPMC), 0, S-dimethyl-N-acetylphosphoramide thioate (acephate), 2-sec-butyl-4,6-dinitrophenyl-3-methylcrotonate ( Binapacryl), tricyclohexyltin hydroxide (plictran), S-4-phenoxybutyl-N, N-dimethylthiocarbamate (phenothiocarb),
[0016]
Insecticides or acaricides such as 2-sec-butylphenyl-N-methylcarbamate (BPMC) and 2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether (ethofenprox) Can be mentioned. In the water-suspended pesticide preparation of the present invention, one or more of these pesticide active ingredients can be used, and a plurality of herbicides, fungicides, insecticides and the like can be mixed.
[0017]
The homopolysaccharide used in the present invention represents a polysaccharide composed of one monosaccharide, and examples thereof include pullulan and curdlan. Pullulan is a linear high molecular weight polysaccharide produced by the fermentation of microorganisms, and the constituent monosaccharide is glucose.
[0018]
The smectite clay mineral materials used in the present invention include natural and synthetic smectite clay minerals. Smectite refers to a group of expansive clay minerals usually obtained by substitution of various metal atoms in the clay structure of granite and talc, such as montmorillonite, saponite, hectorite, bentonite, beidellite, nontronite, saucolite. , Stepensite and the like can be exemplified, and montmorillonite and bentonite are preferable.
[0019]
These smectite clay minerals include, for example, Veegum T, Veegum B, Bangel B (registered trademark, manufactured by Vander Build), Laponite B, Laponite RD, Laponite S (registered trademark, manufactured by Nippon Silica Industry Co., Ltd.), Kunigel VA, Kunigel V1, Kunipia F (Kunimine Industry Co., Ltd., registered trademark), San Bentonite KA-1, San Bentonite KG-1 (Sun Bentonite Industry Co., Ltd., registered trademark), Osmos N (Shiraishi Industry Co., Ltd., It is marketed under a trade name such as a registered trademark.
[0020]
The blending amounts of the homopolysaccharide and smectite clay mineral used in the present invention are usually about 0.5 to 3% by weight in this agent, respectively, and the viscosity of the preparation is 10 to 200 mPa.s. What is necessary is just to adjust each compounding quantity so that it may become s.
Further, the mixing ratio of the homopolysaccharide and the smectite clay mineral is preferably in the range of 0.5 to 5 homopolysaccharide, particularly preferably 1 with respect to the smectite clay mineral 1 by weight. ~ 3.
[0021]
The water sol of the present invention is obtained by suspending or partially dissolving the above-mentioned agrochemical substance, homopolysaccharide and smectite clay mineral in an aqueous solvent. As the aqueous solvent, water or a solution obtained by adding another organic solvent to water is used. The compounding quantity of an aqueous solvent is 30 to 95 weight% in this sol agent.
[0022]
The storage stability of the water-suspended agricultural chemical preparation of the present invention is further improved by further using a heteropolysaccharide gum and / or carboxymethylcellulose in combination with the above composition. The heteropolysaccharide gum used in the present invention represents a polysaccharide composed of two or more monosaccharides, and examples thereof include xanthan gum, welan gum, guar gum, locust bean gum, and lambzan gum.
[0023]
Xanthan gum is a linear high molecular weight polysaccharide produced by the fermentation of microorganisms. The molecular weight is about 2 million, and the constituent monosaccharides consist of glucose, mannose and glucuronic acid.
[0024]
The carboxymethyl cellulose used in the present invention is a homopolysaccharide derivative containing a carboxymethyl group, and preferably has a substitution degree of the carboxymethyl group of anhydroglucose in the range of 0.6 to 1.5. The compounding quantities of the heteropolysaccharide gum and carboxymethyl cellulose used in the present invention are usually about 0.01 to 3% by weight, preferably 0.05 to 1% by weight, respectively, in the present sol.
[0025]
Further, a surfactant may be used in combination with the water-suspended agricultural chemical formulation of the present invention. As the surfactant to be used, any known and commonly used nonionic surfactants and anionic surfactants can be used without limitation.
[0026]
Specific examples of nonionic surfactants include polyoxyethylene aryl phenyl ether, polyoxyethylene alkyl aryl ether, sucrose fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene sorbitan alkylate, polyoxyethylene alkyl ester, polyoxyethylene An alkyl ether etc. can be mentioned.
[0027]
Specific examples of the anionic surfactant include lignin sulfonate, alkylaryl sulfonate, polyoxyethylene arylphenyl ether phosphate ester, polyoxyethylene arylphenyl ether sulfate ester, polyoxyethylene alkylphenyl ether Examples thereof include phosphoric acid esterified salts, dioctyl sulfosuccinate, polycarboxylate and the like.
[0028]
These surfactants may be used singly or in combination of two or more of different or similar surfactants in an arbitrary ratio. It is particularly preferable to use a nonionic surfactant and an anionic surfactant in combination from the viewpoint of suspension stability and dispersibility in water. The blending amount is usually 1 to 10% by weight of the water-suspended agricultural chemical preparation.
[0029]
In the present invention, a commonly used and commonly used thickener other than the above-mentioned homopolysaccharide, smectite clay mineral, heteropolysaccharide gum and methylcellulose can be added within a range not impairing the effects of the present invention. Examples of the thickener include methyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone, silicon oxide, aluminum oxide and the like.
[0030]
The water-suspended agricultural chemical formulation of the present invention may further contain additives such as an antifoaming agent and an antifreezing agent, if necessary, in addition to the above components. As the antifoaming agent, for example, silicon-based ones are used, and as the antifreezing agent, for example, diols such as ethylene glycol and diethylene glycol, glycol ethers, urea and the like are preferably used.
[0031]
The water-suspended agricultural chemical formulation of the present invention has a viscosity of 10 to 200 mPa.s at 20 ° C. for easy handling and use. If the viscosity is in this range, the remaining amount in the container is small when the drug product is taken out, the drug can be used without waste, accurate weighing is possible, and dispersion in water is possible. In addition to its excellent properties, it can be made into a low-viscosity formulation that has good nozzle permeability when spraying the stock solution during spraying in the air and the like, and enables a certain amount of drug spraying.
[0032]
In addition, the viscosity said here is rotor No. using B type rotational viscometer (BM type, Tokyo Keiki Co., Ltd. make). 3. The measured viscosity under the measurement conditions of a rotor rotational speed of 60 rpm and a drug product temperature of 20 ± 0.4 ° C.
[0033]
When homopolysaccharide is used alone in a water suspension formulation, a formulation with good storage stability cannot be obtained, and when a smectite clay mineral is used alone, the viscosity increases with time. Therefore, a favorable result cannot be obtained. Further, when the smectite clay mineral substance and carboxymethylcellulose are used in combination, the viscosity increases with time, and the water dispersibility deteriorates accordingly.
[0034]
In the present invention, by using a homopolysaccharide and a smectite clay mineral in combination, or by further using a heteropolysaccharide gum and / or carboxymethylcellulose, it has excellent storage stability and a good physical property of low viscosity. can get.
[0035]
Next, the outline of the manufacturing method of the sol agent of this invention is shown.
First, a homopolysaccharide and a smectite clay mineral are added to a predetermined amount of an aqueous solvent and dispersed with a stirrer, and then a surfactant and an agrochemical base are added. Further, if necessary, an antifreezing agent, an antifoaming agent, etc. are added and mixed and dispersed with a stirrer.
[0036]
Next, most of the agrochemical raw material is mixed with a wet pulverizer such as a Dynomill KDL type (manufactured by WAB), a system zeta LMZ type (manufactured by Ashizawa Corporation), a pearl mill TEX type (manufactured by Ashizawa Corporation), Is 10 μm or less, preferably wet pulverized so as to have an average particle size in the range of 0.1 to 7 μm, to obtain a target water-suspended agricultural chemical formulation (sol).
[0037]
The order of adding the auxiliary raw materials such as the agrochemical raw material and the surfactant may be appropriately changed depending on the process convenience such as foaming, but the homopolysaccharide and the smectite clay mineral are sufficiently dispersed in an aqueous solvent in advance. Alternatively, it is preferable to dissolve the surfactant, and it is preferable to add the surfactant after dispersing or dissolving the agrochemical raw material.
[0038]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited only to the said Example. The following “parts” represents “parts by weight”.
[0039]
[Example 1]
1 part of pullulan and 1 part of Kunipia F are mixed and dispersed in 78.3 parts of water, and 0.6 parts of polyoxyethylene arylphenyl ether (manufactured by Takemoto Yushi Co., Ltd.) and polyoxyethylene arylphenyl ether sulfate ester salt are added thereto. (Toho Chemical Industries Co., Ltd.) 1.0 part was added and mixed and dissolved, then 12 parts of pyributycarb base, 0.1 part of modified silicone emulsion and 6 parts of ethylene glycol were added and pulverized with a wet pulverizer. A homogeneous water-suspended agricultural chemical formulation (sol) was obtained.
[0040]
[Example 2]
2 parts of pullulan and 1 part of Kunipia F were mixed and dispersed in 77.1 parts of water. To this, 0.8 part of sucrose fatty acid ester (manufactured by Takemoto Yushi Co., Ltd.), polyoxyethylene arylphenyl ether phosphate ester (Toho) (Chemical Industry Co., Ltd.) 1.0 part and 1 part of polycarboxylate were added and mixed and dissolved, and then 12 parts of pyributicarb base, 0.1 part of modified silicone emulsion and 6 parts of ethylene glycol were added, and a wet pulverizer To obtain a homogeneous sol.
[0041]
[Example 3]
3 parts of pullulan and 1 part of Kunipia F were mixed and dispersed in 76.1 parts of water, and 0.8 parts of polyoxyethylene / polyoxypropylene tristyryl phenyl ether (Rhone-Poulenc Co., Ltd.) and polyoxyethylene nonylphenyl ether phosphorus were mixed therein. After adding 1.0 part of acid esterified salt (Matsumoto Yushi Co., Ltd.) and mixing and dissolving, 12 parts of pyributibalb base, 0.1 part of modified silicone emulsion and 6 parts of ethylene glycol are added, and wet milling is performed. By grinding, a homogeneous sol was obtained.
[0042]
[Example 4]
2 parts of pullulan, 1 part of Kunipia F and 0.05 part of xanthan gum are mixed and dispersed in 77.25 parts of water, and 0.6 part of polyoxyethylene / polyoxypropylene block polymer (manufactured by Takemoto Yushi Co., Ltd.) is added thereto. After adding 1.0 part of arylphenyl ether phosphate ester salt (same as above) and mixing and dissolving, 12 parts of pyributicarb base, 0.1 part of modified silicone emulsion and 6 parts of ethylene glycol are added and wet milling is performed. By grinding, a homogeneous sol was obtained.
[0043]
[Example 5]
2 parts of pullulan, 1 part of Kunipia F and 0.1 part of carboxymethylcellulose are mixed and dispersed in 77.2 parts of water, and 0.6 parts of polyoxyethylene nonylphenyl ether (manufactured by Matsumoto Yushi Co., Ltd.) and polyoxyethylene arylphenyl are mixed therewith. After adding 1.0 part of ether phosphate ester salt (same as above) and mixing and dissolving, 12 parts of pyributibalb base, 0.1 part of modified silicone emulsion and 6 parts of ethylene glycol are added and pulverized with a wet pulverizer. A homogeneous sol was obtained.
[0044]
[Example 6]
2 parts of pullulan, 1 part of Kunipia F, and 0.2 part of carboxymethylcellulose are mixed and dispersed in 77.1 parts of water, and 0.6 parts of polyoxyethylene arylphenyl ether (Rhone-Poulenc Co., Ltd.) is added thereto. After adding 1.0 part of ether phosphate ester salt (same as above) and mixing and dissolving, 12 parts of pyributibalb base, 0.1 part of modified silicone emulsion and 6 parts of ethylene glycol are added and pulverized with a wet pulverizer. A homogeneous sol was obtained.
[0045]
[Example 7]
1.5 parts of curdlan and 1 part of Kunipia F were mixed and dispersed in 77.8 parts of water, and 0.6 parts of polyoxyethylene / polyoxypropylene block polymer monooleate (manufactured by Matsumoto Yushi Co., Ltd.), polyoxyethylene After adding 1.0 part of arylphenyl ether phosphate ester salt (same as above) and mixing and dissolving, 12 parts of pyributicarb base, 0.1 part of modified silicone emulsion and 6 parts of ethylene glycol are added and wet milling is performed. By grinding, a homogeneous sol was obtained.
[0046]
[Example 8]
2 parts of pullulan, 1 part of Kunipia F and 0.1 part of carboxymethylcellulose are mixed and dispersed in 66.2 parts of water, and 0.6 part of polyoxyethylene arylphenyl ether (same as above) is converted to polyoxyethylene arylphenyl ether sulfate. After adding 1.0 part of a salt (same as above) and 1 part of a sodium alkylaryl sulfonate copolymer and mixing and dissolving, 10 parts of a pyributycarb base, 1 part of bifenox, 12 parts of bromobutide, 0.1 part of a modified silicone emulsion and 6 parts of ethylene glycol was added and pulverized with a wet pulverizer to obtain a homogeneous sol.
[0047]
[Example 9]
2 parts of pullulan, 1 part of Kunipia F and 0.2 part of carboxymethylcellulose were mixed and dispersed in 73.5 parts of water, and 0.8 parts of sucrose fatty acid ester (same as above), polyoxyethylene arylphenyl ether sulfate ester salt ( Same as above) After adding 1.0 part and mixing and dissolving, 10 parts of pyributicarb base, 4 parts of tenyl chlor base, 1.4 parts of bensulfuron methyl, 0.1 part of modified silicone emulsion and 6 parts of ethylene glycol are added, A homogeneous sol was obtained by pulverization with a wet pulverizer.
[0048]
[Comparative Example 1]
In the same manner as in Example 1 except that 1 part of pullulan and 1 part of Kunipia F in Example 1 were replaced with 3 parts of pullulan and 78.3 parts of water were changed to 77.3 parts, Obtained.
[0049]
[Comparative Example 2]
In the same manner as in Example 1 except that 1 part of pullulan and 1 part of Kunipia F1 of Example 1 were replaced with 1 part of Kunipia and 78.3 parts of water was changed to 79.3 parts, a homogeneous sol agent of pyributicarb was obtained. Obtained.
[0050]
[Comparative Example 3]
A homogeneous sol agent of pyributicarb was obtained in the same manner as in Example 1 except that 1 part of pullulan and 1 part of Kunipia F1 of Example 1 were replaced with 2 parts of Kunipia F2.
[0051]
[Comparative Example 4]
A homogeneous sol of pyributicarb was obtained in the same manner as in Example 1 except that 1 part of pullulan and 1 part of Kunipia F1 of Example 1 were replaced with 3 parts of Kunipia F, and 78.3 parts of water were changed to 77.3 parts. It was.
[0052]
[Comparative Example 5]
A homogeneous sol of pyributicarb in the same manner as in Example 1 except that 1 part of pullulan and 1 part of Kunipia F in Example 1 were replaced with 0.1 part of xanthan gum and 78.3 parts of water were changed to 80.2 parts. Got.
[0053]
[Comparative Example 6]
A homogeneous sol agent of pyributycarb was obtained in the same manner as in Example 1 except that 1 part of pullulan in Example 1 was replaced with 0.05 part of xanthan gum and 78.3 parts of water was changed to 79.25 parts.
[0054]
[Comparative Example 7]
In the same manner as in Example 1 except that 1 part of pullulan and 1 part of Kunipia F in Example 1 were replaced with 0.05 part of xanthan gum and 2 parts of Kunipia F, and 78.3 parts of water was changed to 78.25 parts. A homogeneous sol was obtained.
[0055]
[Comparative Example 8]
In the same manner as in Example 1, except that 1 part of pullulan and 1 part of Kunipia F in Example 1 were replaced with 1 part of colloidal silicon oxide and 2 parts of Kunipia F, and 78.3 parts of water were changed to 77.3 parts. A homogeneous sol was obtained.
[0056]
[Comparative Example 9]
A homogeneous sol of pyributicarb in the same manner as in Example 1 except that 1 part of pullulan and 1 part of Kunipia F of Example 1 were replaced with 3 parts of colloidal aluminum oxide and 78.3 parts of water were changed to 77.3 parts. An agent was obtained.
[0057]
[Comparative Example 10]
A homogeneous sol of pyributicarb in the same manner as in Example 1 except that 1 part of pullulan and 1 part of Kunipia F in Example 1 were replaced with 3 parts of colloidal silicon oxide and 78.3 parts of water were changed to 77.3 parts. An agent was obtained.
[0058]
[Comparative Example 11]
A homogeneous sol of pyributicarb in the same manner as in Example 1 except that 1 part of pullulan and 1 part of Kunipia F in Example 1 were replaced with 0.3 part of carboxymethylcellulose and 78.3 parts of water were changed to 80.0 parts. An agent was obtained.
[0059]
Next, Test Examples 1 to 4 performed on the sol agents prepared in Examples 1 to 9 and Comparative Examples 1 to 11 are shown below. The test results are shown in Tables 1 and 2. * In Table 2 indicates the occurrence of aggregation. From the results shown in Tables 1 and 2, it can be seen that the sols of the examples show better storage stability and dispersibility than those of the comparative examples, have low viscosity, and good handling properties.
[0060]
(Test Example 1) Measurement of storage stability The prepared sol agent was placed in a 500 ml glass bottle and stored in a constant temperature oven at 40 ° C for 3 months, and the separation and sedimentation property of the sol agent was measured. The measurement was calculated by the ratio (%) of the height of the supernatant to the height of the whole liquid. Moreover, after the measurement was completed, the presence or absence of the formation of aggregates was confirmed using an optical microscope (× 400) and a particle size distribution measuring device (LS230: manufactured by Coulter). The storage stability is better as the proportion of the supernatant is smaller, and the formation of aggregates is unsuitable as a sol agent.
[0061]
Test Example 2 Viscosity Measurement After the glass bottle of the sol used in Test Example 1 was inverted 10 times, the viscosity was measured. For measurement, a B-type viscometer (BM type, manufactured by Tokyo Keiki Co., Ltd.) was used. 3. Performed at a rotor rotation speed of 60 rpm and a formulation temperature of 20 ± 0.4 ° C. The viscosity is better as the change with time is smaller.
[0062]
(Test Example 3) Dispersibility in water 250 ml of water was placed in a 250 ml graduated cylinder, the sol was dropped by a pipette, the dispersion state was observed, and the following four stages of evaluation were performed. The better the dispersion state, the better.
[0063]
A: The dispersion state is very good. The drug disperses so that it diffuses in the water.
○: The dispersion state is good. The drug falls in the form of droplets while partially diffusing in the water, but is dispersed by the time it reaches the bottom.
(Triangle | delta): A dispersion state is a little bad. Most of the drug falls to the bottom in the form of droplets, but is dispersed by shaking the graduated cylinder.
X: The dispersion state is bad. The drug falls to the bottom in the form of droplets and does not disperse easily when the graduated cylinder is shaken.
[0064]
(Test Example 4) Measurement of remaining amount of container 100 g of sol was placed in a general 100 ml polyethylene container for storing liquid pesticides, and the ratio (%) of the remaining amount of the container was measured. In the method, after the polyethylene container was inverted 10 times, the container was inverted for 10 seconds, the sol was taken out, and the ratio was calculated from the remaining amount of the polyethylene container minus its own weight. The smaller the remaining amount of the container, the better.
[0065]
[Table 1]
Figure 0003746831
[0066]
[Table 2]
Figure 0003746831
[0067]
【The invention's effect】
In the present invention, (1) almost no sedimentation separation occurs even when stored for a long period of time, and hard caking and aggregates are not formed. {Circle around (2)} The viscosity is low and the wet grinding efficiency at the time of use improves, so that productivity is improved and filling and packaging into a storage container is easy.
In addition, since it can be accurately weighed during use, a stable control effect can be obtained, the amount of chemical solution remaining in the container can be easily confirmed, the dispersibility in water is good, and the spray solution can be easily prepared. In addition to the effects such as no clogging in the spraying device in the spraying of the stock solution in the air or direct sowing spraying, stable drug spraying is possible, and the remaining amount of chemical solution in the container is small after use. 3 ▼ Low viscosity region, that is, 100 mPa.s Even at a viscosity of s or less, an excellent water-suspended agricultural chemical formulation having good viscosity characteristics and storage stability over a long period of time can be provided.

Claims (4)

1種又は2種以上の水難溶性農薬原体と、プルラン又はカードランと、スメクタイト系粘土鉱物質とを含有することを特徴とする水懸濁状農薬製剤。A water-suspended pesticide formulation comprising one or two or more poorly water-soluble pesticide active ingredients, pullulan or curdlan, and a smectite clay mineral. ヘテロポリサッカライドガムを併用することを特徴とする請求項1に記載の水懸濁状農薬製剤。  The water-suspended agricultural chemical formulation according to claim 1, wherein a heteropolysaccharide gum is used in combination. カルボキシメチルセルロースを併用することを特徴とする請求項1又は2に記載の水懸濁状農薬製剤。  Carboxymethylcellulose is used in combination, The water-suspended agricultural chemical formulation according to claim 1 or 2. 水懸濁状農薬製剤の粘度が室温で10〜200mPa.sであることを特徴とする請求項1、2又は3に記載の水懸濁状農薬製剤。The water-suspended agricultural chemical formulation according to claim 1 , 2 or 3 , wherein the viscosity of the water-suspended agricultural chemical formulation is 10 to 200 mPa.s at room temperature.
JP08373496A 1996-04-05 1996-04-05 Aqueous pesticide formulation Expired - Fee Related JP3746831B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP08373496A JP3746831B2 (en) 1996-04-05 1996-04-05 Aqueous pesticide formulation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP08373496A JP3746831B2 (en) 1996-04-05 1996-04-05 Aqueous pesticide formulation

Publications (2)

Publication Number Publication Date
JPH09278602A JPH09278602A (en) 1997-10-28
JP3746831B2 true JP3746831B2 (en) 2006-02-15

Family

ID=13810764

Family Applications (1)

Application Number Title Priority Date Filing Date
JP08373496A Expired - Fee Related JP3746831B2 (en) 1996-04-05 1996-04-05 Aqueous pesticide formulation

Country Status (1)

Country Link
JP (1) JP3746831B2 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5119625B2 (en) * 2006-08-10 2013-01-16 住友化学株式会社 Aqueous suspension pesticide composition
CN101511171B (en) 2006-09-12 2015-11-25 日本曹达株式会社 Stable suspension noxious organism control agent
JP5075158B2 (en) * 2009-04-23 2012-11-14 日立アロカメディカル株式会社 Liquid medicine dispensing device
JP2012051871A (en) * 2010-08-03 2012-03-15 Nissan Chem Ind Ltd Aqueous suspended agrochemical composition
JP5763958B2 (en) * 2011-04-07 2015-08-12 北興化学工業株式会社 Aqueous suspension formulation with improved shelf life
JP6390838B2 (en) * 2013-08-08 2018-09-19 日産化学株式会社 Aqueous suspension pesticide composition

Also Published As

Publication number Publication date
JPH09278602A (en) 1997-10-28

Similar Documents

Publication Publication Date Title
US7674476B1 (en) Use of aerogels in agriculture
JPS5998002A (en) Liquid agricultural drug composition in form of suspension concentrate
JPS6058881B2 (en) Stable aqueous suspension pesticide composition
JPH01117805A (en) Aqueous suspension concentrate composition of pendimethalin
JP3746831B2 (en) Aqueous pesticide formulation
TW200820900A (en) Herbicidal composition
JPS62212303A (en) Granular destroying agent composition
JP3705857B2 (en) Aqueous pesticide formulation
KR950006924B1 (en) Stabilized-aqueous pesticidal suspension concentrate
JP2688822B2 (en) Pesticide composition in suspension
JP2017075144A (en) Aqueous suspended agrochemical composition
JP2002363005A (en) Stabilized agricultural aqueous suspension
JPS6358801B2 (en)
JP2011079741A (en) Aqueous suspension-like agrochemical composition
JPH01175902A (en) Suspension-like agricultural chemical composition
JP3499376B2 (en) Aqueous suspension pesticide stabilizer and aqueous suspension pesticide
WO1999066792A1 (en) Pesticide preparations in the form of aqueous suspension
JP2926495B2 (en) Suspended pesticide composition
JPS60104002A (en) Stable aqueous suspended pesticide
JPH06256122A (en) Agrichemical composition suspended in water
JPH09124406A (en) Granulated water dispersible powder
JP2932600B2 (en) Suspended agricultural fungicide composition
JPS5824401B2 (en) Antennarukendakujiyounoyaku
JP3313016B2 (en) Aqueous suspension pesticide formulation and suspension stabilizer
JPH11255602A (en) Suspended state agrochemical composition and its production

Legal Events

Date Code Title Description
A711 Notification of change in applicant

Free format text: JAPANESE INTERMEDIATE CODE: A711

Effective date: 20040622

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20050701

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20050719

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20050829

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: 20051115

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20051125

R150 Certificate of patent or registration of utility model

Free format text: JAPANESE INTERMEDIATE CODE: R150

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

Free format text: PAYMENT UNTIL: 20091202

Year of fee payment: 4

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

Free format text: PAYMENT UNTIL: 20091202

Year of fee payment: 4

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

Free format text: PAYMENT UNTIL: 20101202

Year of fee payment: 5

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

Free format text: PAYMENT UNTIL: 20101202

Year of fee payment: 5

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

Free format text: PAYMENT UNTIL: 20111202

Year of fee payment: 6

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

Free format text: PAYMENT UNTIL: 20111202

Year of fee payment: 6

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

Free format text: PAYMENT UNTIL: 20121202

Year of fee payment: 7

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

Free format text: PAYMENT UNTIL: 20121202

Year of fee payment: 7

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

Free format text: PAYMENT UNTIL: 20131202

Year of fee payment: 8

LAPS Cancellation because of no payment of annual fees