JP2515541B2 - Pesticide powder - Google Patents
Pesticide powderInfo
- Publication number
- JP2515541B2 JP2515541B2 JP62089313A JP8931387A JP2515541B2 JP 2515541 B2 JP2515541 B2 JP 2515541B2 JP 62089313 A JP62089313 A JP 62089313A JP 8931387 A JP8931387 A JP 8931387A JP 2515541 B2 JP2515541 B2 JP 2515541B2
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- powder
- pesticide
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Description
【発明の詳細な説明】 産業上の利用分野 本発明は、改良された農薬粉剤に関する。更に詳しく
は、農薬活性成分及び鉱物質粉状担体に、炭化水素系粘
稠液体の一種から数種を配合することにより飛散性が抑
えられる等の改良がなされた農薬粉剤に関する。TECHNICAL FIELD OF THE INVENTION The present invention relates to improved pesticide powders. More specifically, the present invention relates to a pesticide dusting agent that is improved in that the scattering property is suppressed by blending one or several kinds of a hydrocarbon-based viscous liquid with a pesticidal active ingredient and a mineral substance powdery carrier.
従来の技術 農薬粉剤の散布の際、目的とする圃場以外の粉剤が飛
散し、他の動植物への悪影響を及ぼすことを避けるた
め、農薬粉剤のドリフト防止が、強く要望されており、
これらの方法として、微粒剤、粗粉剤のような、粗大粒
へと粒度を調整した剤型にするか、あるいは、流動パラ
フィン、ポリブテン、ポリイソブテン等の湿潤性物質等
を添加する方法が知られており、例えば、特公昭53−23
383及び特公昭55−37521等に、後者の方法が提案されて
いる。Conventional technology When spraying pesticide powder, dust powder from areas other than the target field is scattered and in order to avoid adversely affecting other plants and animals, prevention of drift of pesticide powder is strongly demanded,
As these methods, there is known a method of forming a dosage form in which the particle size is adjusted to coarse particles such as a fine granule and a coarse powder, or adding a wettable substance such as liquid paraffin, polybutene and polyisobutene. For example, Japanese Patent Publication No. 53-23
The latter method is proposed in 383 and Japanese Examined Patent Publication No. 55-37521.
発明が解決しようとする問題点 しかし、これらのドリフト防止方法のうち、特に前者
の方法では、特殊な造粒装置が必要となり、又粗大粒に
造粒された農薬は、作物等の表面に付着しにくく、かつ
吸収されにくいという欠点があり、効果を奏し始めるの
に時間を要する。その間風雨により流失される可能性も
あり、更に効果が低下することは免れない。Problems to be Solved by the Invention However, among these drift prevention methods, the former method in particular requires a special granulation device, and the pesticides granulated into coarse particles adhere to the surface of crops or the like. It has a drawback that it is hard to do and is not easily absorbed, and it takes time to start producing the effect. During that time, there is a possibility that it will be washed away by wind and rain, and the effect will inevitably decline.
又、後者の方法は、流動性、分散性、吐粉性及び付着
性等の物性を失うことなく、かつ農薬活性成分のドリフ
トを抑制できるという要求を、十分に充たししかも経済
的にも有利な方法とは言い難かった。Further, the latter method sufficiently satisfies the requirement that the drift of the agrochemical active ingredient can be suppressed without losing the physical properties such as fluidity, dispersibility, dusting property and adhesiveness, and is economically advantageous. It was hard to say how.
而して特殊な装置も要せず、低コストで扱い易く、粉
剤自体の流動性、付着性等の物性を失うことなく、しか
もそれ自体毒性等安全面で問題のない、ドリフト防止の
為の添加剤が要望されていた。Therefore, it does not require special equipment, is easy to handle at low cost, does not lose the physical properties such as fluidity and adhesiveness of the powder itself, and has no safety problems such as toxicity itself, for the purpose of drift prevention. Additives were desired.
本発明の目的は、農薬活性成分のドリフトを、効率的
で、経済的にも有利な方法で抑制し得る農薬粉剤を提供
することにある。An object of the present invention is to provide a pesticide dusting agent capable of suppressing drift of a pesticide active ingredient in an efficient and economically advantageous manner.
問題点を解決するための手段 本発明は、前記のような農薬粉剤中の農薬活性成分の
ドリフト防止のための添加剤を種々検討した結果、エチ
レンとα−オレフィンのコオリゴマー及びイソブチレン
のオリゴマーあるいは、これに更に塩素化パラフィンを
加えたものを、農薬活性物質及び鉱物質粉状担体に配合
した場合、流動性、分散性、吐粉性及び付着性等を失う
ことなく活性成分の飛散性、浮遊性が、顕著に低減され
ることを見出す一方、意外にも農薬活性成分の安定性が
改良され、その結果薬効が向上するという予想外の効果
も奏することも見出して本発明を完成するに至った。Means for Solving the Problems The present invention has variously studied additives for preventing drift of the agrochemical active ingredient in the agrochemical powder as described above, as a result, ethylene and α-olefin co-oligomers and isobutylene oligomers or , If chlorinated paraffin is further added to this, when blended with a pesticide active substance and a mineral powder carrier, the flowability, dispersibility, scattering property of the active ingredient without losing the adhesiveness, etc., While finding that the floating property is remarkably reduced, surprisingly the stability of the pesticide active ingredient is improved, and as a result, it is also found that an unexpected effect that the drug efficacy is improved is also completed, and the present invention is completed. I arrived.
すなわち、本発明はエチレンとα−オレフィンのコオ
リゴマー及びイソブチレンのオリゴマーあるいは、これ
に更に塩素化パラフィンを加えたものを、含有すること
を特徴とする農薬粉剤であり、本発明の農薬粉剤は、か
かる炭化水素系粘稠液体の添加により、農薬活性成分の
飛散性、浮遊性が低減し、更には、農薬活性成分の貯蔵
時の分解が防がれ、ひいては農薬としての薬効が向上
し、生物効果が優れているという特徴を有する。That is, the present invention is a pesticide powder characterized by containing ethylene and α-olefin cooligomers and isobutylene oligomers, or those to which chlorinated paraffin is further added, and the pesticide powder of the present invention, By the addition of such a hydrocarbon-based viscous liquid, the scattering and floating properties of the pesticide active ingredient are reduced, further, the decomposition of the pesticide active ingredient during storage is prevented, which in turn improves the medicinal effect as a pesticide, and It is characterized by its excellent effect.
本発明に用いられる、前記炭化水素系粘稠液体につい
て以下に詳述する。エチレンとα−オレフィンのコオリ
ゴマーとしては、例えば （式中ＲはCnH2n+1でx,y,p及びｎは、30≦x,y≦70,5≦
ｐ≦8,n＝１〜３の整数を表す）で表わされるオリゴマ
ーが好都合に用いられる。上記式において、ｎ＝1,x＝
ｙ＝50及びｐ＝10〜60を満たす構造を有するものがより
好ましく、就中、ルーカント （HC−10,HC−20,HC−4
0,HC−100,HC−150,HC−600及びHC−2000の各銘柄を含
む，三井石油化学工業（株）製）が、特に好ましい。 Regarding the above-mentioned hydrocarbon-based viscous liquid used in the present invention,
The details will be described below. Ethylene and α-olefin Koori
As gommer, for example(In the formula, R is CnH2n + 1, x, y, p and n are 30 ≦ x, y ≦ 70,5 ≦
oligomer represented by p ≦ 8, n = 1 to 3)
Is conveniently used. In the above formula, n = 1, x =
Those having a structure satisfying y = 50 and p = 10 to 60 are more preferable.
Preferably, among others, Lucant (HC-10, HC-20, HC-4
0, HC-100, HC-150, HC-600 and HC-2000
Mu, manufactured by Mitsui Petrochemical Industry Co., Ltd. is particularly preferable.
イソブチレンのオリゴマーとしては、例えば （式中、２≦ｎ≦10）で表わされるオリゴマーが好まし
く、就中、例えば、IPソルベント−2835（数平均分子量
270）及びIPソルベント−2028（数平均分子量220）［と
もに出光石油化学（株）製］が、好都合に用いられる。
これに更に加えて用いてもよい添加剤である塩素化パラ
フィンは、パラフィンを塩素化して得られる液体であ
り、例えば、パラフィンワックスあるいは低分子ノルマ
ルパラフィンを原料に、塩素を含有量40〜70％で含有
し、比重1.10〜1.70、平均分子量350〜1100のものが好
都合に用いられ、好ましくは、トヨパラックス ［東洋
曹達工業（株）製］、更に好ましくは、トヨパラックス
Ａ−40、トヨパラックス145及びトヨパラックス150,
［塩素含有量は、それぞれ40.5％,43.5％,50％，比重は
それぞれ1.16（25℃）,1.16（25℃）及び1.25（25
℃）］の銘柄が用いられる。 As the isobutylene oligomer, for example,An oligomer represented by the formula (2 ≦ n ≦ 10) is preferable.
In particular, for example, IP Solvent-2835 (number average molecular weight
270) and IP Solvent-2028 (number average molecular weight 220) [and
Manufactured by Idemitsu Petrochemical Co., Ltd.] is conveniently used.
Chlorinated paraffin, which is an additive that may be used in addition to this
Fins are liquids obtained by chlorinating paraffin.
For example, paraffin wax or low molecular weight normal
Containing 40 to 70% chlorine with the raw material of paraffin
However, it is preferable to have a specific gravity of 1.10 to 1.70 and an average molecular weight of 350 to 1100.
Conveniently used, preferably Toyoparax [Orient
Soda Kogyo Co., Ltd.], and more preferably Toyoparax
A-40, Toyo Parax 145 and Toyo Parax 150,
[Chlorine content is 40.5%, 43.5%, 50% respectively, and specific gravity is
1.16 (25 ℃), 1.16 (25 ℃) and 1.25 (25 ℃)
℃)] is used.
これら添加剤の添加量は、特に制限されないが、単独
に添加される場合は、当該添加剤の添加量が、複数添加
される場合は、その併せた添加量が粉剤100重量部に対
して0.1ないし10重量部好ましくは0.2ないし5.0重量部
使用するのが特に効果的である。The addition amount of these additives is not particularly limited, when added alone, the addition amount of the additive, when a plurality is added, the combined addition amount is 0.1 to 100 parts by weight of dusting agent. It is particularly effective to use 10 to 10 parts by weight, preferably 0.2 to 5.0 parts by weight.
本発明において、使用される農薬活性成分は殺虫，殺
菌，除草などの活性を有するもので、施用時ドリフト性
を軽減させる必要のある農薬粉剤ならば、すべて本発明
の技術を適用することが出来、特に制限はされないが、
例えば次のような化合物があげられる。ビスチオリン酸
O,O−ジメチル＝Ｏ−４−ニトロ−ｍ−トリル，フェ
ニルホスホノチオン酸Ｏ−エチル＝Ｏ−ｐ−ニトロフェ
ニル，チオリン酸Ｏ−2,3−ジヒドロ−３−オキソ−２
−フェニル−６−ピリダジニル＝O,O−ジエチル，ジチ
オリン酸Ｓ−1,2−ビス（エトキシカルボニル）エチル
＝O,O−ジメチル，ジチオリン酸 Ｓ−［α−（エトキ
シカルボニル）ベンジル］＝O,O−ジメチル，ジチオリ
ン酸O,O−ジメチル＝Ｓ−（Ｎ−メチルカルバモイルメ
チル）,N−アセチルホスホロアミドチオール酸 O,S−
ジメチル（以下アセフェートと称する）,2,2,2−トリク
ロロ−１−ヒドロキシエチルホスホン酸ジメチル，メチ
ルカルバミド酸 Ｏ−sec−ブチルフェニル（以下BPMC
と称する），メチルカルバミド酸１−ナフチル，メチル
カルバミド酸ｍ−トリル，メチルカルバミド酸Ｏ−クメ
ニル（以下MIPCと称する），ビス（チオカルバミン酸）
S,S′−［２−（ジメチルアミノ）トリメチレン］（以
下カルタップと称する），テトラクロロイソフタロニト
リル，チオリン酸 Ｓ−ベンジル＝O,O−ジイソプロピ
ル，ジチオリン酸,O−エチル＝S,S−ジフェニル，ブラ
ストサイジンS,カスガマイシン，バリダマイシンA,S,
S′−２−ジメチルアミノトリメチレンジ（ベンゼンチ
オスルホネート）（以下ベンスルタップと略称する）,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（以下エトフェンプロック
スを略称する），リン酸２−クロロ−１−（2,4−ジク
ロロフェニル）ビニル＝ジエチル等があげられる。しか
し本発明はこれらの例示に制限されるものではない。又
これらは適宜目的に応じて単独で用いても又二種以上を
組み合せて用いてもよい。これら活性成分は通常、単独
で用いる場合は、当該単価の活性成分の使用量が複数種
を併用する場合は、その全量が粉剤100重量部に対し0.0
001ないし50重量部、好ましくは0.001ないし20重量部用
いられるが、その使用量は特に制限されるものではな
い。In the present invention, the pesticide active ingredient used has activity such as insecticidal, bactericidal, weeding, etc., and the technique of the present invention can be applied to all pesticide powders that need to reduce driftability during application. , Is not particularly limited,
For example, the following compounds may be mentioned. Bisthiophosphoric acid
O, O-dimethyl = O-4-nitro-m-tolyl, O-ethyl phenylphosphonothionate = Op-nitrophenyl, thiophosphoric acid O-2,3-dihydro-3-oxo-2
-Phenyl-6-pyridazinyl = O, O-diethyl, S-1,2-bis (ethoxycarbonyl) ethyl dithiophosphate = O, O-dimethyl, dithiophosphate S- [α- (ethoxycarbonyl) benzyl] = 0, O-dimethyl, dithiophosphoric acid O, O-dimethyl = S- (N-methylcarbamoylmethyl), N-acetylphosphoramidothioic acid O, S-
Dimethyl (hereinafter referred to as acephate), dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate, O-sec-butylphenyl methylcarbamate (hereinafter referred to as BPMC
1-naphthyl methylcarbamate, m-tolyl methylcarbamate, O-cumenyl methylcarbamate (hereinafter referred to as MIPC), bis (thiocarbamic acid)
S, S '-[2- (dimethylamino) trimethylene] (hereinafter referred to as cartap), tetrachloroisophthalonitrile, thiophosphate S-benzyl = O, O-diisopropyl, dithiophosphoric acid, O-ethyl = S, S- Diphenyl, blasticidin S, kasugamycin, validamycin A, S,
S'-2-Dimethylaminotrimethylene di (benzenethiosulfonate) (hereinafter abbreviated as bensultap), 2
-(4-Ethoxyphenyl) -2-methylpropyl 3-
Phenoxybenzyl ether (hereinafter abbreviated as etophene prox), 2-chloro-1- (2,4-dichlorophenyl) vinyl phosphate = diethyl and the like can be mentioned. However, the present invention is not limited to these examples. These may be used alone or in combination of two or more depending on the purpose. These active ingredients are usually used alone, when the amount of the monovalent active ingredient used is a combination of two or more, the total amount is 0.0 with respect to 100 parts by weight of the dust.
The amount used is 001 to 50 parts by weight, preferably 0.001 to 20 parts by weight, but the amount used is not particularly limited.
鉱物質粉状担体成分としては特に制限はされないがよ
り具体的には、たとえばクレイ、カオリン、ベントナイ
ト、酸性白土、タルク類（滑石粉，ロウ石粉など），シ
リカ類（ホワイトカーボン，硅藻土，雲母粉など）及び
炭酸カルシウムが繁用される。The mineral powder carrier component is not particularly limited, but more specifically, for example, clay, kaolin, bentonite, acid clay, talc (talc powder, wax stone powder, etc.), silicas (white carbon, diatomaceous earth, Mica powder) and calcium carbonate are frequently used.
本発明の農薬粉剤には上記添加剤による効果をそこな
わない安定剤，展着剤，防腐剤等を適宜加えてもよい。
このような安定剤としては、例えば、リン酸，イソプロ
ピルアシドホスフェート［日本化学（株）製、以下PAP
と称する］,EDTA（エチレンジアミン四酢酸），エポキ
シ化アマニ油，チオ尿素，ホウ酸等が、防腐剤として
は、ソルビン酸，ソルビン酸カリウム，デハイドロ酢
酸，デハイドロ酢酸ナトリウム塩,p−オキシ安息香酸ブ
チルエステル等が又、展着剤としては、アルキルベンゼ
ンスルホン酸塩，ジオクチルスルホコハク酸ナトリウム
塩，ポリオキシエチレンアルキルエーテル等がそれぞれ
挙げられる。Stabilizers, spreading agents, preservatives and the like which do not impair the effects of the above additives may be added to the pesticide powder of the present invention as appropriate.
Examples of such stabilizers include phosphoric acid, isopropyl acid phosphate [manufactured by Nippon Kagaku Co., Ltd., hereinafter PAP
, EDTA (ethylenediaminetetraacetic acid), epoxidized linseed oil, thiourea, boric acid, etc., as preservatives, sorbic acid, potassium sorbate, dehydroacetic acid, sodium dehydroacetate, butyl p-oxybenzoate. Examples of the spreading agent include esters such as alkylbenzene sulfonate, sodium dioctylsulfosuccinate, and polyoxyethylene alkyl ether.
本発明の農薬粉剤は、例えば、次のように製造され
る。The agricultural chemical powder of the present invention is produced, for example, as follows.
鉱物質粉状担体、及び農薬活性成分に、本発明の前記
炭化水素系粘性稠液体を適宜注加して、混合する。次い
で、鉱物質粉状担体並びに／又は、増量・希釈剤を適量
加えて、更に混合し、粗粉砕して農薬粉剤を得る。上記
混合においては、例えば、ナウターミキサー（細川ミク
ロン（株）製）が、好ましく用いられ、又粗粉砕に際し
ては、例えば、ハンマーミキサーが好都合に用いられ
る。The above hydrocarbon-based viscous viscous liquid of the present invention is appropriately added to and mixed with the mineral powder carrier and the agrochemical active ingredient. Then, an appropriate amount of a mineral powder carrier and / or an extender / diluent is added, further mixed and coarsely pulverized to obtain an agricultural chemical powder. In the above mixing, for example, a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.) is preferably used, and in coarse pulverization, for example, a hammer mixer is conveniently used.
作用 本発明において、添加される前記炭化水素系粘性稠液
体は、農薬粉剤に湿潤性を与え、特にドリフト発生に問
題となる10μ以下の粒子の飛散や浮遊を完全に抑えられ
る。更に、本発明においては、粒子を粗大に造粒する等
の手段は施こす必要はなく、かつ前記特定添加剤はいず
れも、粉剤の流動性，分散性，付着性を著しくそこなう
ことなく、これら農薬粉剤として必要な、粉体物性を満
たすため、適宜粒度を下げることも可能である。Action In the present invention, the above-mentioned hydrocarbon-based viscous viscous liquid imparts wettability to the pesticide powder, and in particular, scattering or floating of particles of 10 μ or less, which is a problem in the occurrence of drift, can be completely suppressed. Furthermore, in the present invention, it is not necessary to apply means such as coarsely granulating the particles, and any of the specific additives described above does not significantly impair the fluidity, dispersibility, and adhesiveness of the powder, In order to satisfy the powder physical properties required as a pesticide powder, the particle size can be appropriately reduced.
一方、農薬活性成分が、不安定な場合、とりわけ、水
に不安定な成分については、本発明の農薬粉剤に適用さ
れた場合、生物活性の向上が著しい。これら水に不安定
な成分は、一般にクレー等の鉱物質粉状担体と混合、接
触した際にこれら担体の付着水分によって分解され易
く、貯蔵安定性や薬効の点で、難点があるが、前記粘稠
液体を添加する本発明の農薬粉剤においては、かかる添
加剤による油膜により活性成分が、保護されクレー等担
体の持つ水による分解が防がれ、安定性が改良される結
果、薬効が向上するものと推察される。On the other hand, when the pesticidal active ingredient is unstable, particularly when it is applied to the pesticide powder of the present invention, the biological activity of the ingredient unstable to water is remarkably improved. These water-unstable components are generally easily decomposed by adhering water of these carriers when mixed and contacted with a mineral powder carrier such as clay, and there are drawbacks in terms of storage stability and medicinal effect. In the pesticide powder of the present invention to which a viscous liquid is added, the active ingredient is protected by the oil film due to such an additive, decomposition by water of the carrier such as clay is prevented, stability is improved, and the drug efficacy is improved. It is presumed to do.
かくして、特にベンスルタップ，カルタップ，アセフ
ェートあるいはバリダマイシン等で代表される水に不安
定な農薬活性成分を含有する農薬粉剤の製造にあたっ
て、本発明を適用した場合にドリフトを抑えかつ生物活
性を改良するという本発明の効果が顕著といえる。Thus, especially in the production of pesticide powders containing a water-unstable pesticide active ingredient represented by bensultap, cartap, acephate, validamycin, etc., a book that suppresses drift and improves biological activity when the present invention is applied. The effect of the invention can be said to be remarkable.
例 以下、本発明の例を説明するが、本発明は例により、
何ら制限されるものではない。Example Hereinafter, an example of the present invention will be described.
It is not limited in any way.
文中単に部とあるのは、すべて重量部を示す。 In the text, "parts" means "parts by weight".
例１ ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー３部及びベンスルタップ原体2.5部を加えIP
ソルベント−2835 0.25部，ルーカントHC−40 0.5部を
注加して５分間混合する。次いでホワイトカーボン0.5
部及び農薬用微粉クレー93.25部を加えて更に10分間混
合し、ハンマーミルで粗粉砕して本発明の農薬粉剤を得
る。Example 1 Add 3 parts of fine clay for agricultural chemicals and 2.5 parts of Bensultap drug substance to a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.) IP
Add 0.25 parts of Solvent-2835 and 0.5 parts of Lucant HC-40 and mix for 5 minutes. Then white carbon 0.5
Parts and 93.25 parts of fine powder clay for agricultural chemicals are added and mixed for another 10 minutes, and coarsely crushed with a hammer mill to obtain the agricultural chemical powder of the present invention.
例２ ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー５部及びベンスルタップ原体2.5部,MIPC原体
2.0部を加えIPソルベント−2835 2.5部，ルーカントHC
−2000 0.30部を注加して５分間混合する。次いでホワ
イトカーボン1.0部,PAP 0.5部及び農薬用微粉クレー86.
2部を加えて更に10分間混合し、ハンマーミルで粗粉砕
して本発明の農薬粉剤を得る。Example 2 5 parts of fine clay for agricultural chemicals, 2.5 parts of Bensultap drug substance, and MIPC drug substance in a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.)
Add 2.0 parts IP Solvent-2835 2.5 parts, Lucant HC
-2000 Add 0.30 parts and mix for 5 minutes. Next is 1.0 part of white carbon, 0.5 part of PAP and 86 of fine powder clay for agricultural chemicals.
Add 2 parts, mix for a further 10 minutes, and roughly crush with a hammer mill to obtain the pesticide powder of the present invention.
例３ ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー3.5部及びベンスルタップ原体2.5部,BPMC原
体3.5部を加えIPソルベント−2835 0.75部，ルーカント
HC−2000 0.4部を注加して５分間混合する。次いでホワ
イトカーボン0.3部,PAP 0.5部及び農薬用微粉クレー88.
55部を加えて更に10分間混合し、ハンマーミルで粗粉砕
して本発明の農薬粉剤を得る。Example 3 To a Nauta Mixer (manufactured by Hosokawa Micron Co., Ltd.), 3.5 parts of fine clay for agricultural chemicals, 2.5 parts of Bensultap drug substance and 3.5 parts of BPMC drug substance were added, and IP Solvent-2835 0.75 part, Lucant
Add 0.4 parts HC-2000 and mix for 5 minutes. Next is 0.3 part of white carbon, 0.5 part of PAP and fine clay for agricultural chemicals88.
After adding 55 parts and further mixing for 10 minutes, coarsely pulverized with a hammer mill to obtain the agricultural chemical powder of the present invention.
例４ ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー２部及びベンスルタップ原体2.0部及びバリ
ダマイシンＡ原体0.3部を加えIPソルベント−2835 1.2
部，ルーカントHC−20 0.55部を注加して５分間混合す
る。次いでホワイトカーボン1.0部及び農薬用微粉クレ
ー94.7部を加えて更に10分間混合し、ハンマーミルで粗
粉砕して本発明の農薬粉剤を得る。Example 4 To a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.) were added 2 parts of fine powder clay for agricultural chemicals, 2.0 parts of Bensultap drug substance and 0.3 part of validamycin A drug substance, and IP Solvent-2835 1.2.
Part, Lucant HC-20 (0.55 part), and mix for 5 minutes. Next, 1.0 part of white carbon and 94.7 parts of fine clay for agricultural chemicals are added, mixed for 10 minutes, and coarsely pulverized with a hammer mill to obtain the agricultural chemical powder of the present invention.
例５ ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー５部及びベンスルタップ原体2.0部並びにエ
トフェンプロックス原体0.5部を加えIPソルベント−283
5 1.5部，ルーカントHC−600 0.75部を注加して５分間
混合する。次いでホワイトカーボン1.5部及び農薬用微
粉クレー88.75部を加えて更に10分間混合し、ハンマー
ミルで粗粉砕して本発明の農薬粉剤を得る。Example 5 To a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.) were added 5 parts of finely divided clay for agricultural chemicals, 2.0 parts of Bensultap drug substance and 0.5 part of etofenprox drug substance, and IP Solvent-283.
5 Add 1.5 parts and 0.75 parts of Lucant HC-600 and mix for 5 minutes. Next, 1.5 parts of white carbon and 88.75 parts of fine clay for agricultural chemicals are added and mixed for another 10 minutes, and coarsely pulverized with a hammer mill to obtain the agricultural chemical powder of the present invention.
例６ ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー3.5部及びベンスルタップ原体2.5部，エトフ
ェンプロックス原体0.5部を加えIPソルベント−2028 2.
0部，ルーカントHC−20 1.5部を注加して５分間混合す
る。次いでホワイトカーボン2.0部及び農薬用微粉クレ
ー88部を加えて更に10分間混合し、ハンマーミルで粗粉
砕して本発明の農薬粉剤を得る。Example 6 To a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.) was added 3.5 parts of fine powdered clay for agricultural chemicals, 2.5 parts of Bensultap drug substance, 0.5 part of etofenprox drug substance, and IP Solvent-2028 2.
Add 0 parts and 1.5 parts of Lucant HC-20 and mix for 5 minutes. Then, 2.0 parts of white carbon and 88 parts of fine powder clay for agricultural chemicals are added and mixed for another 10 minutes, and coarsely crushed by a hammer mill to obtain the agricultural chemical powder of the present invention.
例７ ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー５部及びベンスルタップ原体2.5部を加えル
ーカントHC−600 3.3部を注加して５分間混合する。次
いでホワイトカーボン1.0部及び農薬用微粉クレー90.7
部を加えて更に10分間混合し、ハンマーミルで粗粉砕し
て本発明の農薬粉剤を得る。Example 7 To a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.), 5 parts of fine clay for pesticide and 2.5 parts of bensultap raw material were added, and 3.3 parts of Lucant HC-600 was added and mixed for 5 minutes. Next, 1.0 part of white carbon and 90.7 of fine powder clay for agricultural chemicals
Parts and then further mixed for 10 minutes and coarsely pulverized with a hammer mill to obtain the agricultural chemical powder of the present invention.
例８ ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー３部及びベンスルタップ原体1.0部,MIPC原体
2.0部を加えIPソルベント−2028 0.3部，ルーカントHC
−600 0.3部及びトヨパラックスＡ−40 1.0部を注加し
て５分間混合する。次いでホワイトカーボン2.0部及び
農薬用微粉クレー90.4部を加えて更に10分間混合し、ハ
ンマーミルで粗粉砕して本発明の農薬粉剤を得る。Example 8 3 parts of fine clay for agricultural chemicals, 1.0 part of Bensultap drug substance, and MIPC drug substance in a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.)
Add 2.0 parts IP Solvent-2028 0.3 parts, Lucant HC
Add 0.3 parts of -600 and 1.0 part of Toyoparax A-40 and mix for 5 minutes. Next, 2.0 parts of white carbon and 90.4 parts of fine powdered clay for agricultural chemicals are added and mixed for another 10 minutes, and coarsely pulverized with a hammer mill to obtain the agricultural chemical powder of the present invention.
例９ ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー３部及びカルタップ塩酸塩原体1.5部を加え
ルーカントHC−40 1.5部，トヨパラックス150 1.0部を
注加して５分間混合する。次いでPAP 0.5部，ホワイト
カーボン2.0部及び農薬用微粉クレー90.5部を加えて更
に10分間混合し、ハンマーミルで粗粉砕して本発明の農
薬粉剤を得る。Example 9 To a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.) were added 3 parts of finely divided clay for agricultural chemicals and 1.5 parts of cartap hydrochloride standard, 1.5 parts of Lucant HC-40 and 1.0 part of Toyoparax were added and mixed for 5 minutes. Next, 0.5 parts of PAP, 2.0 parts of white carbon and 90.5 parts of fine powdered clay for agricultural chemicals are added and mixed for another 10 minutes, and coarsely pulverized with a hammer mill to obtain the agricultural chemical powder of the present invention.
例10 ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー３部及びカルタップ塩酸塩原体2.5部,MIPC原
体2.5部を加えプロセスオイルPS−32 2部及びトヨパラ
ックス145 0.8部を注加して５分間混合する。次いでホ
ワイトカーボン1.5部及び農薬用微粉クレー87.7部を加
えて更に10分間混合し、ハンマーミル粗粉砕して本発明
の農薬粉剤を得る。Example 10 To a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.), 3 parts of fine-powder clay for agricultural chemicals, 2.5 parts of Cartap hydrochloride raw material and 2.5 parts of MIPC raw material were added, and 2 parts of process oil PS-32 and 0.8 parts of Toyoparax 145 were added. And mix for 5 minutes. Then, 1.5 parts of white carbon and 87.7 parts of fine powder clay for agricultural chemicals are added and further mixed for 10 minutes, and coarsely crushed with a hammer mill to obtain the agricultural chemical powder of the present invention.
例11 ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー３部及びカルタップ塩酸塩原体1.5部,BPMC原
体2.0部を加えプロセスオイルNM−280 1.2部及びルーカ
ントHC−10 0.5部を注加して５分間混合する。次いでホ
ワイトカーボン1.3部及び農薬用微粉クレー90.5部を加
えて更に10分間混合し、ハンマーミルで粗粉砕して本発
明の農薬粉剤を得る。Example 11 To a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.) was added 3 parts of fine clay for agricultural chemicals, 1.5 parts of Cartap hydrochloride raw material, 2.0 parts of BPMC raw material, and 1.2 parts of process oil NM-280 and 0.5 parts of Lucant HC-10. Add and mix for 5 minutes. Next, 1.3 parts of white carbon and 90.5 parts of fine powdered clay for agricultural chemicals are added and mixed for another 10 minutes, and coarsely pulverized with a hammer mill to obtain the agricultural chemical powder of the present invention.
例12 ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー３部及びカルタップ塩酸塩原体2.0部，エト
フェンプロックス原体0.5部を加えNISSO−PB B−2000
0.5部及びNISSO−PB G−1000 0.75部を注加して５分間
混合する。次いでホワイトカーボン1.2部及び農薬用微
粉クレー92.05部を加えて更に10分間混合し、ハンマー
ミルで粗粉砕して本発明の農薬粉剤を得る。Example 12 To a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.) were added 3 parts of fine clay for agricultural chemicals, 2.0 parts of Cartap hydrochloride raw material, 0.5 parts of etofenprox raw material, and NISSO-PB B-2000.
Add 0.5 parts and 0.75 parts NISSO-PBG-1000 and mix for 5 minutes. Next, 1.2 parts of white carbon and 92.05 parts of fine clay for agricultural chemicals are added and mixed for another 10 minutes, and coarsely pulverized with a hammer mill to obtain the agricultural chemical powder of the present invention.
例13 ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー３部及びベンスルタップ原体2.5部,MIPC原体
2.5部を加えNISSO−PB C−1000 0.8部及びIPソルベント
−2835 0.85部を注加して５分間混合する。次いでホワ
イトカーボン1.5部及び農薬用微粉クレー88.85部を加え
て更に10分間混合し、ハンマーミルで粗粉砕して本発明
の農薬粉剤を得る。Example 13 3 parts of fine clay for pesticides and 2.5 parts of Bensultap drug substance, MIPC drug substance in a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.)
Add 2.5 parts of NISSO-PBC-1000 0.8 parts and IP Solvent-2835 0.85 parts and mix for 5 minutes. Next, 1.5 parts of white carbon and 88.85 parts of finely divided clay for agricultural chemicals are added and mixed for 10 minutes, and coarsely pulverized with a hammer mill to obtain the agricultural chemical powder of the present invention.
例14 ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー３部及びカルタップ塩酸塩原体2.5部を加えI
Pソルベント−2835 0.25部，ルーカントHC−40 0.5部を
注加してPAP 0.5部を加え５分間混合する。次いでホワ
イトカーボン0.5部及び農薬用微粉クレー93.25部を加え
て更に10分間混合し、ハンマーミルで粗粉砕して本発明
の農薬粉剤を得る。Example 14 To a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.) was added 3 parts of fine-powder clay for agricultural chemicals and 2.5 parts of cartap hydrochloride standard I
Add 0.25 parts of P-solvent-2835 and 0.5 parts of Lucant HC-40, add 0.5 parts of PAP, and mix for 5 minutes. Next, 0.5 part of white carbon and 93.25 parts of fine clay for agricultural chemicals are added and mixed for 10 minutes, and coarsely crushed by a hammer mill to obtain the agricultural chemical powder of the present invention.
次に、本発明の効果を更に詳述するために、本発明に
属さない下記製剤と比較した試験例を示す。Next, in order to further elaborate the effects of the present invention, test examples are shown in comparison with the following preparations which do not belong to the present invention.
対照製剤例１ ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー３部及びベンスルタップ原体2.5部を加え流
動パラフィン［WITCO Chemical Corporation（米国）
製］0.75部を注加して５分間混合する。次いでホワイト
カーボン0.5部及び農薬用微粉クレー93.25部を加えて更
に10分間混合し、ハンマーミルで粗粉砕して農薬粉剤を
得る。Control Formulation Example 1 To a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.) was added 3 parts of finely divided clay for agricultural chemicals and 2.5 parts of bensultap raw material, and liquid paraffin [WITCO Chemical Corporation (US)]
Manufactured] 0.75 parts are added and mixed for 5 minutes. Next, 0.5 parts of white carbon and 93.25 parts of fine powdered clay for agricultural chemicals are added and mixed for another 10 minutes, and coarsely ground with a hammer mill to obtain a agricultural chemical powder.
対照製剤例２ ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー５部及びベンスルタップ原体2.5部,MIPC原体
2.0部を加えポリブテン（銘柄100H;出光石油化学（株）
製）2.8部を注加して５分間混合する。次いでホワイト
カーボン1.0部,PAP 0.5部及び農薬用微粉クレー86.2部
を加えて更に10分間混合し、ハンマーミルで粗粉砕して
農薬粉剤を得る。Control formulation example 2 5 parts of fine clay for pesticides and 2.5 parts of Bensultap drug substance, MIPC drug substance in a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.)
Added 2.0 parts of polybutene (brand 100H; Idemitsu Petrochemical Co., Ltd.)
2.8 parts) and mixed for 5 minutes. Next, 1.0 part of white carbon, 0.5 part of PAP and 86.2 parts of fine powdered clay for pesticides are added and mixed for another 10 minutes, and coarsely pulverized with a hammer mill to obtain pesticide powders.
対照製剤例３ ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー５部及びベンスルタップ原体2.5部,MIPC原体
2.0部を加え流動パラフィン［WITCO Chemical Corporat
ion（米国）製］2.8部を注加して５分間混合する。次い
でホワイトカーボン1.0部,PAP 0.5部及び農薬用微粉ク
レー86.2部を加えて更に10分間混合し、ハンマーミルで
粗粉砕して農薬粉剤を得る。Control formulation example 3 A Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.) was used, and 5 parts of fine clay for agricultural chemicals and 2.5 parts of Bensultap drug substance and MIPC drug substance were used.
Add 2.0 parts of liquid paraffin [WITCO Chemical Corporat
Ion (USA)] 2.8 parts are added and mixed for 5 minutes. Next, 1.0 part of white carbon, 0.5 part of PAP and 86.2 parts of fine powdered clay for pesticides are added and mixed for another 10 minutes, and coarsely pulverized with a hammer mill to obtain pesticide powders.
対照製剤例４ ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー５部及びベンスルタップ原体2.5部を加え流
動パラフィン［WITCO Chemical Corporation（米国）
製］3.3部を注加して５分間混合する。次いでホワイト
カーボン1.0部及び農薬用微粉クレー88.2部を加えて更
に10分間混合し、ハンマーミルで粗粉砕して農薬粉剤を
得る。Control formulation example 4 To a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.) was added 5 parts of fine clay for agricultural chemicals and 2.5 parts of bensultap raw material, and liquid paraffin [WITCO Chemical Corporation (US)]
[Production] Add 3.3 parts and mix for 5 minutes. Next, 1.0 part of white carbon and 88.2 parts of fine powdered clay for agricultural chemicals are added and mixed for another 10 minutes, and coarsely crushed with a hammer mill to obtain a agricultural chemical powder.
対照製剤例５ ナウターミキサー（細川ミクロン（株）製）に農薬用
微粉クレー５部，カルタップ塩酸塩原体2.5部を加え流
動パラフィン［WITCO Chemical Corporation（米国）
製］0.75部を注加して５分間混合する。次いでホワイト
カーボン0.5部及び農薬用微粉クレー98.25部を加えて更
に10分間混合し、ハンマーミルで粗粉砕して農薬粉剤を
得る。Control Formulation Example 5 Liquid paraffin [WITCO Chemical Corporation (US)] was added to a Nauta Mixer (manufactured by Hosokawa Micron Co., Ltd.) with 5 parts of fine clay for agricultural chemicals and 2.5 parts of cartap hydrochloride standard.
Manufactured] 0.75 parts are added and mixed for 5 minutes. Next, 0.5 parts of white carbon and 98.25 parts of fine powdered clay for agricultural chemicals are added and mixed for another 10 minutes, and coarsely crushed with a hammer mill to obtain a agricultural chemical powder.
試験例１ 浮遊性指数 農薬粉剤を圃場で散布した時見掛の飛散性を定量的に
表現するため、昭和55年10月３日付にて農林水産省農薬
検査所より指示された「DL粉剤新規申請に必要な提出資
料について」に記載の浮遊性指数測定法により浮遊性指
数を測定し、その結果を表１に示した。Test Example 1 Suspension index In order to quantitatively express the apparent scattering properties of pesticide dust applied in the field, "DL dust powder new" was instructed by the Ministry of Agriculture, Forestry and Fisheries pesticide laboratory on October 3, 1980. The floating index was measured by the floating index measuring method described in "About materials to be submitted for application" and the results are shown in Table 1.
試験例２ 有効成分の飛散性 試験例１で浮遊性を測定した同じ装置を用いて試料を
散布し、５分後に同装置内の上部（底から140cm）から
空気を30l吸引し、有効成分を捕集し定量して、有効成
分の飛散性を調べその結果を表２に示した。 Test Example 2 Scattering of active ingredient The sample was sprayed using the same device whose buoyancy was measured in Test Example 1, and after 5 minutes, 30 l of air was sucked from the top (140 cm from the bottom) in the same device to remove the active ingredient. The results are shown in Table 2 by collecting and quantifying to examine the scattering of the active ingredient.
試験例３ 有効成分の安定性 例に示した本発明による改良された農薬粉剤及び対照
製剤をそれぞれ40℃恒温器中で30日及び60日間保管した
後、有効成分含量を測定し、分解率を求め、その結果を
表３に示した。 Test Example 3 Stability of Active Ingredient The improved pesticide powder and control formulation of the present invention shown in the examples were stored in a 40 ° C. incubator for 30 days and 60 days, respectively, and the active ingredient content was measured to determine the decomposition rate. The results are shown in Table 3.
試験例４ 殺虫効力試験 10,000分の１アールのポットに植えた移植50日後（草
丈60cm）のイネ（品種中生新千本）をベルジャーダスタ
ー（内径30cm,高さ50cm）内に立て、真空ポンプで60cmH
gに減圧して散布した。散布後２時間してイネの茎葉部
を切り取りポリカップ（内径10.5cm,高さ6cm）に入れそ
こへアワヨトウ幼虫（３令）をイネ１株当り10頭を放ち
殺虫効力を調べ表４に示した。 Test Example 4 Insecticidal test 50 days after transplanting (60 cm plant height) rice (variety: Nakamiso new 1000) planted in a pot of 1 / 10,000 are are placed in a bell jar duster (inner diameter 30 cm, height 50 cm) and vacuum pumped. 60 cmH
The pressure was reduced to g and sprayed. Two hours after spraying, the foliage of rice was cut out and placed in a polycup (inner diameter 10.5 cm, height 6 cm), and 10 larvae of armyworm (3rd instar) were released to each rice plant and the insecticidal efficacy was shown in Table 4. .
本発明による改良製剤の浮遊性指数は表１に示す通り
良好である。本発明者らは更に研究を続け、有効成分の
飛散性についても測定上の工夫をこらし測定した結果、
表２に示した通り、本発明の改良製剤は、飛散性が顕著
に改善されており、有効成分の植物体への付着性良好な
ことがわかる。このことは表３に示す本発明品の有効成
分の分解率が少ないことと合わせて、本発明の改良粉剤
の殺虫効力が高まった原因と推察される。 The floatability index of the improved formulation according to the present invention is good as shown in Table 1. The present inventors further researched, the results of measuring the scattering of the active ingredient by devising a measure for measurement,
As shown in Table 2, it can be seen that the improved preparation of the present invention has remarkably improved scattering properties and good adhesion of the active ingredient to plants. This is considered to be the cause of the increased insecticidal efficacy of the improved powder of the present invention, together with the low decomposition rate of the active ingredient of the present invention shown in Table 3.
発明の効果 前記試験例からも明らかなように特定粘稠性液体を含
有する本発明の農薬粉剤は、人や家畜をはじめ動植物に
対する悪影響が問題となっているドリフトを、粒度を調
節することにより防止する方法あるいは、流動パラフィ
ンやポリブテン等を添加して、抑止する従来の方法に比
べ、低コストで植物体上での付着性，展着性，吸収性が
そこなわれることなく、優れた生物活性を有し、かつ飛
散性，浮遊性を低減してドリフトが抑えられるという効
果を有する。加えて、本発明の農薬粉剤は農薬活性成分
の分解が防止され、貯蔵安定性や薬効が向上するという
予想外の効果も有する。Effects of the Invention As is clear from the test examples, the pesticide powder of the present invention containing a specific viscous liquid, drift that adverse effects on animals and plants including humans and livestock are a problem, by adjusting the particle size. Compared with the conventional method of preventing or adding liquid paraffin or polybutene, etc., it is an excellent organism without lowering the adhesion, spreadability and absorption on the plant at low cost. It is active and has the effect of suppressing drift by reducing scattering and floating properties. In addition, the pesticide powder of the present invention has an unexpected effect of preventing decomposition of the pesticide active ingredient and improving storage stability and medicinal effect.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ａ０１Ｎ 57/28 Ａ０１Ｎ 57/28 Ａ 63/02 63/02 Ａ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display area A01N 57/28 A01N 57/28 A 63/02 63/02 A
Claims (4)
レンのオリゴマーおよび、エチレンとα−オレフィンの
コオリゴマーを含有することを特徴とする農薬粉剤。1. A pesticide powder comprising an active ingredient of a pesticide, a mineral powder carrier, an isobutylene oligomer, and an ethylene / α-olefin cooligomer.
の範囲第一項記載の農薬粉剤。2. The pesticide powder according to claim 1, which further contains chlorinated paraffin.
である特許請求の範囲第一項または第二項記載の農薬粉
剤。3. The pesticide powder according to claim 1 or 2, wherein the pesticide active ingredient is a water-unstable pesticide active ingredient.
−ジメチルアミノトリメチレンジ（ベンゼンチオスルホ
ネート）、ビス（チオカルバミン酸）S,S′−［２−
（ジメチルアミノ）トリメチレン］、Ｎ−アセチルホス
ホロアミドチオール酸O,S−ジメチルまたはバリダマイ
シンＡである特許請求の範囲第三項記載の農薬粉剤。4. A pesticide active ingredient which is unstable to water is S, S'-2.
-Dimethylaminotrimethylene di (benzenethiosulfonate), bis (thiocarbamic acid) S, S '-[2-
(Dimethylamino) trimethylene], N-acetylphosphoramidothiolic acid O, S-dimethyl, or validamycin A. The agricultural chemical powder according to claim 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8626686 | 1986-04-14 | ||
| JP61-86266 | 1986-04-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6345203A JPS6345203A (en) | 1988-02-26 |
| JP2515541B2 true JP2515541B2 (en) | 1996-07-10 |
Family
ID=13882015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62089313A Expired - Fee Related JP2515541B2 (en) | 1986-04-14 | 1987-04-10 | Pesticide powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2515541B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101032256B (en) * | 2007-04-13 | 2010-06-02 | 彭国均 | Pesticide of composite jinggangmycin |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2706247B1 (en) * | 1993-06-16 | 1996-10-11 | Sumitomo Chemical Co | Method for stabilizing pesticidal compositions containing acephate, and pesticidal compositions obtained. |
| JP2000079004A (en) | 1998-06-23 | 2000-03-21 | Tokai Rika Co Ltd | Buckle |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57159701A (en) * | 1981-03-27 | 1982-10-01 | Hokko Chem Ind Co Ltd | Improved dust of agricultural chemical |
-
1987
- 1987-04-10 JP JP62089313A patent/JP2515541B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101032256B (en) * | 2007-04-13 | 2010-06-02 | 彭国均 | Pesticide of composite jinggangmycin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6345203A (en) | 1988-02-26 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |