JP2010047544A - Finely-powdered pesticide composition - Google Patents
Finely-powdered pesticide composition Download PDFInfo
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本発明は、水などで希釈することなく、散布機などを用いてそのまま散布する固型製剤であり、薬剤散布時の飛散（ドリフト）が改良された微粒状農薬組成物に関するものである。 The present invention relates to a solid pharmaceutical composition that is sprayed as it is using a spreader or the like without being diluted with water or the like, and relates to a fine pesticide composition with improved scattering (drift) during spraying of the drug.
薬剤散布時の飛散が少なく、植物体への薬剤の付着性が良好である製剤として、微粒剤（粒度分布が３００μｍ〜１０６μｍ）および微粒剤Ｆ（粒度分布が２１２μｍ〜６３μｍ）のような微粒状農薬組成物が知られており、これまで、以下に例示されるような多くの報告がなされている。例えば、
（１）固型担体７９〜９９重量％、補助剤０．５〜２０重量％及び除草活性成分０．５〜３．５重量％を含有する粒度４８〜１５０メッシュの微粒型除草剤において、除草活性成分が固型担体の表面層に固着し、水分の存在下に溶出度１％以上で溶出することを特徴とする微粒型除草剤（特許文献１）
（２）粒状担体に農薬活性成分を被覆せしめるのに、有機イソシアネート及び非イオン界面活性剤を含有する水乳化型イソシアネート化合物を使用することを特徴とする被覆型農園芸用粒剤の製造法（特許文献２）
（３）平均粒径が１００〜２００メッシュで、６５メッシュ以上のものを含まない粒度構成を有する無吸油性鉱物質担体６０〜８０％に、粉末状農薬と水溶性結合剤とを加え、水で混練後、破砕と乾燥を行うことを特徴とし、その９０％以上が６５〜２５０メッシュの粒度で、かつ３００メッシュ以下の粒度を含まず、安息角が４５度以下である微粒状農園芸用組成物の製造法（特許文献３）
（４）コーティング時の助剤としてトリクロルエチレン、トリクロルエタンまたはパークロルエチレンあるいはこれらの２種以上の混合物を添加することを特徴とするコーティング型微粒状農薬製剤の製造法（特許文献４）
（５）粒度分布が粒径４４μｍ以下６０〜８０％および粒径２１０μｍ〜４４μｍが４０〜２０％からなり、かつ実質的に２１０μｍ以上の区分を含まない担体を用いて農薬有効成分とともに造粒することを特徴とする２１０μｍ〜６２μｍの粒径範囲内にある微粒状農薬の製造方法（特許文献５）
（６）粒径１００μｍ以下の非吸収性、非孔質粉体を担体として農薬有効成分とともに造粒し実質的に３００μｍ〜４０μｍの粒径を有することを特徴とする農園芸用茎葉散布剤（特許文献６）
（７）非吸収性担体を基剤とし、有効成分１重量部に対してドデシルベンゼンスルホン酸カルシウム０．０５〜２．０重量部を用いて被覆することによりなる有効成分の剥離防止効果を有する微粒状または粗粉状製剤（特許文献７）
（８）非吸収性もしくは比較的非吸収性の鉱物質粒状物と、その上に展着している有効成分および酢酸ビニル重合体ないし共重合体を含む展着層とからなることを特徴とする農園芸用粒状組成物（特許文献８）
（９）鉱物質担体、補助剤および農薬有効成分を適量の水の存在下で造粒して微粒状農薬を製造する方法において、鉱物質担体として実質的に粒径２５０μｍ以上の粒状物を含まず、粒径２５０μｍ〜４４μｍの粗粉及至微粒状物４０〜８５％と粒径４４μｍ以下の粉状物６０〜１５％とからなる担体を使用することを特徴とする粒径２９７μｍ〜１０５μｍの微粒状農薬の製造方法（特許文献９）
（１０）４８メッシュ篩を通過する鉱物質粒状担体に、農薬活性成分と撥水性物質またはこれらと拡展造膜性物質とを担持させてなることを特徴とする改良された微粒状農薬製剤（特許文献１０）
（１１）農薬活性成分を３００メッシュ以上の微粉状鉱物質と補助剤とより造粒した粒径０．１〜０．３ｍｍの微粒状担体に直接又は希釈して吸着させるか、又は付着剤と共に被覆させたことを特徴とする水の存在下で崩壊し、かつ散布中飛散のない微粒状農薬組成物（特許文献１１）
（１２）製剤中に単糖類、二糖類またはその糖アルコール類を含有することを特徴とする実質的に粒径３００μｍ〜４０μｍの農園芸用固体散布剤（特許文献１２）
（１３）製剤表面をポリアクリル酸アルカリ塩、ポリアクリル酸アンモニウム塩、ポリアクリル酸アマイド、ポリアクリル酸アマイドの部分加水分解物及びポリエチレンオキサイドから選ばれた微粉末状固着剤の１種又は２種以上で被覆することを特徴とする改良された農園芸用固体散布剤（特許文献１３）
（１４）分子量２００〜２５０００のポリオキシアルキレンポリオールあるいはこれらのエーテルまたはエステルの一種または二種以上の混合物を製剤に対して０．５〜７．０％含有してなる粒径２９７μｍ〜１０５μｍの付着性良好な微粒状農薬組成物（特許文献１４）などが知られている。
Fine preparations such as fine granules (particle size distribution: 300 μm to 106 μm) and fine granules F (particle size distribution: 212 μm to 63 μm) as preparations with little scattering when spraying the drug and good adhesion of the drug to the plant body Agrochemical compositions are known, and many reports have been made so far as exemplified below. For example,
(1) In a fine herbicide having a particle size of 48 to 150 mesh containing 79 to 99% by weight of a solid carrier, 0.5 to 20% by weight of an adjuvant and 0.5 to 3.5% by weight of a herbicidal active ingredient, A fine herbicide characterized in that the active ingredient adheres to the surface layer of the solid carrier and elutes at a dissolution rate of 1% or more in the presence of moisture (Patent Document 1)
(2) A method for producing a coated agricultural and horticultural granule characterized in that a water-emulsified isocyanate compound containing an organic isocyanate and a nonionic surfactant is used to coat an agrochemical active ingredient on a granular carrier ( Patent Document 2)
(3) A powdery pesticide and a water-soluble binder are added to an oil-absorptive mineral carrier having an average particle size of 100 to 200 mesh and a particle size composition not including 65 mesh or more, and water is added. After being kneaded, the mixture is crushed and dried, 90% or more of which has a particle size of 65 to 250 mesh, does not contain a particle size of 300 mesh or less, and has an angle of repose of 45 degrees or less. Method for producing composition (Patent Document 3)
(4) A method for producing a coated fine particulate pesticide preparation characterized by adding trichlorethylene, trichloroethane, perchlorethylene or a mixture of two or more thereof as an auxiliary agent during coating (Patent Document 4)
(5) Granulate with an agrochemical active ingredient using a carrier whose particle size distribution is 60 to 80% of particle size 44 μm or less and 40 to 20% of particle size 210 μm to 44 μm and does not substantially contain 210 μm or more. A method for producing a fine pesticide within a particle size range of 210 μm to 62 μm (Patent Document 5)
(6) Agricultural and horticultural foliage spraying agent characterized by being granulated with an agrochemical active ingredient using a non-absorbable, non-porous powder having a particle size of 100 μm or less as a carrier and having a particle size of substantially 300 μm to 40 μm ( Patent Document 6)
(7) Based on a non-absorbable carrier and having an effect of preventing peeling of the active ingredient by coating with 0.05 to 2.0 parts by weight of calcium dodecylbenzenesulfonate with respect to 1 part by weight of the active ingredient. Fine or coarse powder formulation (Patent Document 7)
(8) It is characterized by comprising a non-absorbing or relatively non-absorbing mineral particulate and a spreading layer containing an active ingredient and a vinyl acetate polymer or copolymer spread thereon. Agricultural and horticultural granular composition (Patent Document 8)
(9) In a method for producing a fine particulate pesticide by granulating a mineral carrier, an adjuvant and an active ingredient of an agricultural chemical in the presence of an appropriate amount of water, the mineral carrier substantially includes a granular material having a particle size of 250 μm or more. A fine particle having a particle size of 297 μm to 105 μm, characterized by using a carrier composed of a coarse powder having a particle size of 250 μm to 44 μm and a fine particle of 40 to 85% and a powdery material having a particle size of 44 μm or less of 60 to 15%. Method for producing pesticide (Patent Document 9)
(10) An improved fine granular pesticide preparation characterized in that an agrochemical active ingredient and a water repellent substance or these and a spread film-forming substance are supported on a mineral granular carrier passing through a 48 mesh sieve. Patent Document 10)
(11) The agrochemical active ingredient is adsorbed directly or diluted to a fine particle carrier with a particle size of 0.1 to 0.3 mm granulated from a finely divided mineral substance of 300 mesh or more and an auxiliary agent, or with an adhesive. A finely divided pesticide composition which is disintegrated in the presence of water and has no scattering during spraying (Patent Document 11)
(12) A solid spray for agricultural and horticultural use having a particle size of 300 μm to 40 μm, characterized in that the preparation contains monosaccharides, disaccharides or sugar alcohols thereof (Patent Document 12)
(13) One or two fine powdery sticking agents selected from polyacrylic acid alkali salt, polyacrylic acid ammonium salt, polyacrylic acid amide, polyacrylic acid amide partial hydrolyzate and polyethylene oxide on the preparation surface Improved solid spraying agent for agriculture and horticulture characterized by covering with the above (Patent Document 13)
(14) Adhesion with a particle size of 297 μm to 105 μm comprising 0.5 to 7.0% of a polyoxyalkylene polyol having a molecular weight of 200 to 25000 or a mixture of two or more of these ethers or esters to the preparation A finely divided pesticide composition (Patent Document 14) having good properties is known.
上記した発明は、粒度分布を３００μｍ〜６３μｍ程度の範囲にすることで、粉剤（粒度が４５μｍ以下）に比べ薬剤散布時の飛散を少なくするものであり、また、補助剤の効果により微粒表面に存在する農薬有効成分の剥離を少なくすることで更に飛散を改良しようとしたものなどである。しかし、微粒表面に有効成分を強固に付着させたとしても、微粒状農薬組成物の散布に通常使用される多口ホースによる散布などでは、散布時の衝撃により微粒表面の有効成分のみが剥離されるだけではなく、場合によっては微粒自体が破壊されることで微粉化されてしまい飛散が発生するなどの問題があり、また、散布時に微粉化されなくても粒度分布３００μｍ〜６３μｍの範囲に粒度分布を調整しただけでは、粉剤よりは改良されてはいるものの、薬剤散布時の風の影響などで微粒自体が飛散してしまうなどの問題があった。
したがって、上記のいずれの発明においても、薬剤散布時の飛散という観点からは決して満足できるものではなく、更なる改良が求められている。
In the above-described invention, by setting the particle size distribution in the range of about 300 μm to 63 μm, the scattering during the spraying of the drug is less than that of the powder (particle size is 45 μm or less). For example, an attempt was made to further improve the scattering by reducing the peeling of the active ingredients of the agricultural chemicals present. However, even if the active ingredient is firmly attached to the fine particle surface, when spraying with a multi-hose hose normally used for spraying the fine agricultural chemical composition, only the active ingredient on the fine particle surface is peeled off due to the impact during spraying. In addition, in some cases, there is a problem that the fine particles themselves are pulverized due to destruction and scattering occurs, and the particle size distribution is in the range of 300 μm to 63 μm even if they are not pulverized at the time of spraying. Although only the distribution is improved, it is improved over the powder, but there is a problem that the fine particles themselves scatter due to the influence of the wind when spraying the drug.
Therefore, in any of the above-mentioned inventions, it is never satisfactory from the viewpoint of scattering at the time of spraying a medicine, and further improvement is required.
本発明は以上のような従来の欠点に鑑み、薬剤散布時の飛散（ドリフト）が少なく、また、作物への付着性が良好な微粒状農薬組成物を提供することを目的としている。 The present invention has been made in view of the above-described conventional drawbacks, and an object thereof is to provide a finely divided agrochemical composition that has less scattering (drift) at the time of spraying a drug and has good adhesion to crops.
本発明者らは、上記課題を解決すべく鋭意検討した。その結果、ａ）微粒状農薬組成物粒子の９０重量％以上が粒径３００μｍ〜６３μｍの範囲内にあり、かつ粒径３００μｍを超える粒子を含むことがなく、ｂ）微粒状農薬組成物の見掛け比重が１．０〜１．８であり、ｃ）微粒状農薬組成物の硬度が９５〜１００％であるという三つの必須構成要件を同時に満たすことにより、従来の微粒状農薬組成物よりも薬剤散布時の飛散（ドリフト）が少なく、また、作物への付着性が良好な微粒状農薬組成物が得られることを見出し、本発明を完成した。すなわち、本発明は以下の内容をその要旨とするものである。
１）農薬活性成分、結合剤および微粒状担体を含有する微粒状農薬組成物であって、ａ）９０重量％以上の粒子の粒度分布が粒径３００μｍ〜６３μｍの範囲内にあり、かつ粒径３００μｍを超える粒子を含むことがなく、ｂ）見掛け比重が１．０〜１．８であり、ｃ）硬度が９５〜１００％であることを特徴とする微粒状農薬組成物。
２）結合剤が、デキストリンであることを特徴とする１）に記載の微粒状農薬組成物。
３）結合剤が、ブドウ糖当量２〜１５のデキストリンであることを特徴とする１）に記載の微粒状農薬組成物。
The present inventors diligently studied to solve the above problems. As a result, a) 90% by weight or more of the finely divided pesticide composition particles are in the range of 300 μm to 63 μm in particle size and do not contain particles exceeding 300 μm in particle size, and b) the appearance of the finely divided pesticide composition The specific gravity is 1.0 to 1.8, and c) the pharmaceutical composition is more effective than the conventional fine pesticide composition by simultaneously satisfying the three essential constituent requirements that the hardness of the fine pesticide composition is 95 to 100%. The present inventors have found that a finely divided pesticide composition having little scattering (drift) during spraying and good adhesion to crops can be obtained. That is, the gist of the present invention is as follows.
1) A particulate pesticidal composition containing an agrochemical active ingredient, a binder and a particulate carrier, a) a particle size distribution of 90% by weight or more of particles is in the range of 300 μm to 63 μm, and the particle size A particulate pesticide composition characterized by not containing particles exceeding 300 μm, b) an apparent specific gravity of 1.0 to 1.8, and c) a hardness of 95 to 100%.
2) The finely divided agricultural chemical composition according to 1), wherein the binder is dextrin.
3) The finely divided agricultural chemical composition according to 1), wherein the binder is dextrin having a glucose equivalent of 2 to 15.
本発明の微粒状農薬組成物は、動力散布機が装着された多口ホースで散布した場合でも、微粒表面の有効成分が剥離することがなく、微粒自体の破壊による微粉化もなく、また、微粒自体の飛散も少ないことから、薬剤散布時の飛散面で非常に優れる。さらに、作物への付着性も優れるため、高い防除効果がもたらされる。 Even when the fine granular agricultural chemical composition of the present invention is sprayed with a multi-hose equipped with a power spreader, the active ingredient on the surface of the fine particles does not peel off, there is no pulverization due to the destruction of the fine particles themselves, Since there is little scattering of the fine particles themselves, it is very excellent on the scattering surface when spraying the drug. Furthermore, since it has excellent adhesion to crops, it provides a high control effect.
以下に、本発明の微粒状農薬組成物についてより詳細に説明する。
＜農薬活性成分について＞
本発明で用いる農薬活性成分は、殺虫剤、殺菌剤、除草剤、植物成長調節剤などの一般に農薬の活性成分として使用されるものであればよい。また、農薬活性成分を2種以上併用しても何らかまわない。このような農薬活性成分としては次のものが挙げられる。
例えば、殺虫剤として、有機リン系（ＭＥＰなど）、カーバメート系、ネオニコチノイド系、ピレスロイド系、クロロニコチニル系、ピリジンアゾメチン系、チオウレア系、オキサダイアジン系、フェニルピラゾール系、ネライストキシン系、ベンゾイルヒドラジド系およびベンゾイルフェニル尿素系の殺虫剤、天然殺虫剤、殺ダニ剤、生物農薬などが挙げられる。
殺菌剤としては、無機銅類、有機銅類、無機硫黄剤、有機硫黄剤、有機リン系、フタリド系、ベンゾイミダゾール系、ジカルボキシイミド系、酸アミド系（フルトラニルなど）、トリアゾール系、イミダゾール系、メトキシアクリレート系、ストロビルリン系、アニリノピリミジン系、ジチオラン系、キノキサリン系、アミノピリミジン系、フェニルピロール系、トリアジン系、シアノアセトアミド系、グアニジン系、ヒドロキシアニリド系の殺菌剤、抗生物質系殺菌剤（カスガマイシンなど）、天然物殺菌剤、生物農薬などが挙げられる。
除草剤としては、フェノキシ酸系、カーバメート系、酸アミド系、尿素系、スルホニルウレア系、ピリミジルオキシ安息香酸系、トリアジン系、ダイアジン系、ダイアゾール系、ピピリジリウム系、ジニトロアニリン系、芳香族カルボン酸系、脂肪酸系、アミノ酸系、ニトリル系、シクロヘキサンジオン系、フェニルフタルイミド系、有機リン系、シネオール系、インダンジオン系、ベンゾフラン系、トリアゾロピリミジン系、オキサジノン系、アリルトリアゾリノン系、イソウラゾール系、ピリミジニルチオフタリド系、無機除草剤、生物農薬などが挙げられる。
なお、これらに含まれる個々の具体的な農薬活性成分は、例えば「農薬ハンドブック２００５年版」（社団法人 日本植物防疫協会、平成１７年１０月１１日発行）、「SHIBUYA INDEX ９th Edition」（平成１３年１２月１５日発行）、「Ｔｈｅ Ｐｅｓｔｉｃｉｄｅ Manual Eleventh Edition」（British Crop Protection Council 発行）などに記載されている。
上記農薬活性成分は、微粒状農薬組成物中に、通常０．０１〜５０重量％、好ましくは０．０５〜２０重量％である。
Below, it demonstrates in detail about the fine-grained agricultural chemical composition of this invention.
<About pesticide active ingredients>
The pesticidal active ingredient used in the present invention may be anything that is generally used as an pesticidal active ingredient, such as insecticide, fungicide, herbicide, plant growth regulator and the like. Moreover, it does not matter even if two or more kinds of pesticidal active ingredients are used in combination. Examples of such agrochemical active ingredients include the following.
For example, as an insecticide, organophosphorus (MEP, etc.), carbamate, neonicotinoid, pyrethroid, chloronicotinyl, pyridineazomethine, thiourea, oxadiazine, phenylpyrazole, nereistoxin Benzoylhydrazide and benzoylphenylurea insecticides, natural insecticides, acaricides, biopesticides and the like.
Bactericides include inorganic copper, organic copper, inorganic sulfur agent, organic sulfur agent, organic phosphorus, phthalide, benzimidazole, dicarboximide, acid amide (such as flutolanil), triazole, imidazole , Methoxyacrylate, strobilurin, anilinopyrimidine, dithiolane, quinoxaline, aminopyrimidine, phenylpyrrole, triazine, cyanoacetamide, guanidine, hydroxyanilide fungicide, antibiotic fungicide ( Kasugamycin), natural product fungicides, biological pesticides and the like.
Herbicides include phenoxy acid, carbamate, acid amide, urea, sulfonylurea, pyrimidyloxybenzoic acid, triazine, diazine, diazole, piperidyllium, dinitroaniline, aromatic carboxylic acid, fatty acid Series, amino acid series, nitrile series, cyclohexanedione series, phenylphthalimide series, organophosphorus series, cineole series, indandione series, benzofuran series, triazolopyrimidine series, oxazinone series, allyltriazolinone series, isourazole series, pyrimidinylthiophthali And inorganic herbicides and biological pesticides.
In addition, specific pesticide active ingredients contained in these include, for example, “Agricultural Chemicals Handbook 2005” (issued by the Japan Plant Protection Association, published on October 11, 2005), “SHIBUYA INDEX 9th Edition” (2001) Issued on Dec. 15, 2000), “The Pesticide Manual Eleventh Edition” (published by British Crop Protection Council).
The above-mentioned pesticidal active ingredient is usually 0.01 to 50% by weight, preferably 0.05 to 20% by weight in the finely divided pesticidal composition.
＜結合剤について＞
本発明で使用できる結合剤は、天然系、半合成系および合成系の水溶性高分子類である。
例えば、天然系の水溶性高分子としては、デンプン、アラビアガム、トラガントガム、グアーガム、マンナン、ペクチン、アルギン酸ナトリウム、ソルビトール、ローカストビーンガム、キサンタンガム、デキストラン、カードラン、プルラン、ゼラチンおよびカゼインなどが挙げられる。
半合成系の水溶性高分子としては、デキストリン、可溶性デンプン、α化デンプン、メチルセルロース、エチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロースおよびヒドロキシプロピルメチルセルロースなどが挙げられる。
合成系の水溶性高分子としては、ポリビニルアルコール、ポリビニルピロリドン、ポリアクリルアミド、ポリアクリル酸ナトリウム、エチレン−アクリル酸共重合体、ポリエチレングリコールおよびポリエチレンオキシドなどが挙げられる。
なお、本発明では、微粒状農薬組成物の飛散性（微粒から有効成分が剥離することに起因）および作物への付着性の面からデキストリンが好ましい。また、デキストリンとしては、下記式（１）で示されるブドウ糖当量（ＤＥ（Dextrose Equivalent））が２〜１５のデキストリンが、飛散性および作物への付着性の面から特に好ましい。
<About the binder>
Binders that can be used in the present invention are natural, semi-synthetic and synthetic water-soluble polymers.
For example, natural water-soluble polymers include starch, gum arabic, tragacanth gum, guar gum, mannan, pectin, sodium alginate, sorbitol, locust bean gum, xanthan gum, dextran, curdlan, pullulan, gelatin and casein. .
Examples of the semi-synthetic water-soluble polymer include dextrin, soluble starch, pregelatinized starch, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and hydroxypropylmethylcellulose.
Examples of the synthetic water-soluble polymer include polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, sodium polyacrylate, ethylene-acrylic acid copolymer, polyethylene glycol and polyethylene oxide.
In addition, in this invention, dextrin is preferable from the surface of the scattering property (it originates in an active ingredient peeling | exfoliating from a fine particle) and the adhesiveness to a crop in a fine-grained agricultural chemical composition. Further, as dextrin, dextrin having a glucose equivalent (DE (Dextrose Equivalent)) represented by the following formula (1) of 2 to 15 is particularly preferable from the viewpoint of scattering property and adhesion to crops.
＜微粒状担体について＞
本発明で使用できる微粒状担体としては、クレー、炭酸カルシウム、タルク、珪砂、ベントナイト、軽石、ゼオライト、セピオライト、珪藻土およびアタパルジャイトなどが挙げられる。微粒状農薬組成物の見掛け比重を１．０〜１．８、硬度を９５〜１００％とするためには、微粒状担体としては特に珪砂が好ましい。
添加量は、微粒状農薬組成物中に通常４０〜９９．８重量％、好ましくは７０〜９９．８重量％である。
<About fine carrier>
Examples of the particulate carrier that can be used in the present invention include clay, calcium carbonate, talc, silica sand, bentonite, pumice, zeolite, sepiolite, diatomaceous earth, and attapulgite. In order to make the apparent specific gravity of the fine pesticide composition 1.0 to 1.8 and the hardness 95 to 100%, quartz sand is particularly preferable as the fine carrier.
The addition amount is usually 40 to 99.8% by weight, preferably 70 to 99.8% by weight in the finely divided pesticide composition.
＜その他の成分について＞
本発明の微粒状農薬組成物には、補助剤として、上記の必須成分のほかに、必要に応じて、界面活性剤、粉状担体（ホワイトカーボン、珪藻土、タルク、ガラス質粉末、酸性白土、ベントナイト、炭酸カルシウム、塩化ナトリウム、塩化カリウム、尿素、乳糖およびグラニュー糖など）、流動性改良剤（イソプロピルアシッドホスフェートなど）、高沸点溶剤（植物油、鉱物油など）、ｐＨ調整剤、有効成分の安定化剤（酸化防止剤および紫外線防止剤など）などを、本発明が有する効果を失わない範囲内で添加することができる。
なお、本発明において使用できる補助剤は、上記の例に限定されるものではない。
<About other ingredients>
In addition to the above-mentioned essential components, the finely particulate pesticide composition of the present invention includes, as necessary, a surfactant, a powder carrier (white carbon, diatomaceous earth, talc, glassy powder, acid clay, Bentonite, calcium carbonate, sodium chloride, potassium chloride, urea, lactose and granulated sugar), fluidity improvers (such as isopropyl acid phosphate), high-boiling solvents (such as vegetable oil and mineral oil), pH adjusters, stable active ingredients An agent such as an antioxidant and an ultraviolet ray inhibitor can be added within a range not losing the effects of the present invention.
In addition, the adjuvant which can be used in this invention is not limited to said example.
＜微粒状農薬組成物の粒度について＞
本発明では、微粒状農薬組成物の９０重量％以上の粒子が、粒度分布３００μｍ〜６３μｍの範囲にあり、かつ３００μｍを超える粒子を含まないように調整することが重要である。微粒状農薬組成物の粒子の大きさが３００μｍを超えると作物への付着性が極度に低減するため、３００μｍを超える粒子は好ましくない。また、６３μｍ未満の粒子は飛散しやすくなるため、微粒状農薬組成物中に１０重量％以下の含有率とするのが好ましいためである。
なお、微粒状農薬組成物の粒度分布は、以下の方法で測定した。
（粒度分布測定方法）
受け皿の上に、内径２００ｍｍ、深さ４５ｍｍの目開き６３μｍの篩を積み、更に目開き３００μｍの篩を積み重ねる。その後、目開き３００μｍの篩上に微粒状農薬組成物５０ｇを入れ蓋をし、ロータップ型篩分け器に装着する。振とう回数２９０ｒ．ｐ．ｍ．、打数１０５ｔ．ｐ．ｍの条件で１０分間篩分けを行い、目開き３００μｍ、６３μｍの各篩上、あるいは６３μｍ篩の下に置いた受け皿の上に残った試料の重量（ｇ）を各々測定し、下記式（２）より３００μｍを超える粒子、３００μｍ〜６３μｍの粒子、６３μｍ未満の粒子の割合（重量％）を求める。
<Regarding the particle size of the finely divided pesticide composition>
In the present invention, it is important to adjust so that 90% by weight or more of the finely divided pesticide composition has a particle size distribution in the range of 300 μm to 63 μm and does not include particles exceeding 300 μm. If the size of the particles of the finely divided pesticide composition exceeds 300 μm, the adhesion to crops is extremely reduced, so particles exceeding 300 μm are not preferred. Moreover, it is because it is preferable to set it as the content rate of 10 weight% or less in a fine-grained agricultural chemical composition, since the particle | grains less than 63 micrometers become easy to fly.
The particle size distribution of the finely divided pesticide composition was measured by the following method.
(Particle size distribution measurement method)
A sieve having an aperture of 63 μm having an inner diameter of 200 mm and a depth of 45 mm is stacked on the tray, and a sieve having an aperture of 300 μm is further stacked. Thereafter, 50 g of the finely divided pesticide composition is put on a sieve having an opening of 300 μm, covered, and attached to a low tap type sieve. Number of shakes 290 r. p. m. , 105 tapping. p. sieving for 10 minutes under the condition of m, and measuring the weight (g) of the sample remaining on each of the sieves having openings of 300 μm and 63 μm, or on the saucer placed under the 63 μm sieve, respectively. ), The ratio (% by weight) of particles exceeding 300 μm, particles of 300 μm to 63 μm, and particles of less than 63 μm is obtained.
＜微粒状農薬組成物の見掛け比重について＞
本発明では、微粒状農薬組成物の見掛け比重を１．０〜１．８とすることが重要である。微粒状農薬組成物の見掛け比重が１．０未満となると、仮に粒度分布を３００μｍ〜６３μｍの範囲に調整したとしても、微粒状農薬組成物自体が風などの影響で飛散しやすくなるためである。なお、飛散性の面からは、見掛け比重を１．２以上とすると更に好ましい。
一方、見掛け比重が重くなると、微粒状農薬組成物の体積が小さくなるために、動力散布機を装着した多口ホースなどの散布器具からの薬剤の吐出時間が短くなり、薬剤が均一散布しにくくなるなどの問題が生じる。よって、均一な散布性の面からは、見掛け比重を１．８以下とするのが好ましい。
なお、微粒状農薬組成物の見掛け比重は、以下の方法で測定した。
（見掛け比重測定方法）
内径５０ｍｍの１００ｍｌ容の金属製円筒容器の２０ｃｍ上に、内径２００ｍｍ、深さ４５ｍｍの目開き３００μｍの篩をおき、篩上に微粒状農薬組成物を適当量入れ、ハケで軽くはき落としながら金属製円筒容器内を満たす。その後、スライドガラスを用いて、金属製円筒容器上部を水平にならし、余剰分の微粒状農薬組成物を除き、金属製円筒容器内の内容物の重量（Ａｇ）を測定し、下記式（３）より微粒状農薬組成物の見掛け比重を求める。
<Apparent specific gravity of fine granular pesticide composition>
In the present invention, it is important that the apparent specific gravity of the finely divided agricultural chemical composition is 1.0 to 1.8. If the apparent specific gravity of the fine pesticide composition is less than 1.0, even if the particle size distribution is adjusted to a range of 300 μm to 63 μm, the fine pesticide composition itself is likely to be scattered due to the influence of wind or the like. . In terms of scattering properties, the apparent specific gravity is more preferably 1.2 or more.
On the other hand, when the apparent specific gravity increases, the volume of the finely divided pesticide composition decreases, so the discharge time of the drug from a spray device such as a multi-hose equipped with a power spreader is shortened, and it is difficult to spray the drug uniformly. The problem of becoming. Therefore, it is preferable that the apparent specific gravity is 1.8 or less from the viewpoint of uniform dispersibility.
In addition, the apparent specific gravity of the fine granular agricultural chemical composition was measured by the following method.
(Apparent specific gravity measurement method)
Place a sieve with an inner diameter of 200 mm and a depth of 45 mm with an opening of 300 μm on a 20-cm 100-ml metal cylindrical container with an inner diameter of 50 mm, put an appropriate amount of the fine pesticide composition on the sieve, and gently scrape it off with a brush. Fill the metal cylindrical container. Then, using a slide glass, level the upper part of the metal cylindrical container, remove the excess fine pesticide composition, measure the weight (Ag) of the contents in the metal cylindrical container, and use the following formula ( 3) Obtain the apparent specific gravity of the finely divided pesticide composition.
＜微粒状農薬組成物の硬度について＞
本発明では、微粒状農薬組成物の硬度を９５〜１００％とすることが重要である。微粒状農薬組成物の硬度が９５％未満となると、動力散布機を装着した多口ホースなどの散布器具で散布した場合、薬剤散布時の衝撃で微粒状農薬組成物自体が破壊され微粉化されてしまい、飛散性が悪くなるという問題が生じるためである。
なお、微粒状農薬組成物の硬度は、以下の方法で測定した。
（硬度測定方法）
内径１００ｍｍ、内深１００ｍｍの磁性ポットに、微粒状農薬組成物１００ｇを入れ、磁性玉（直径３０ｍｍ、重量３５ｇ）３個を入れた後、磁性ポットの蓋をする。回転ローラー上に、磁性ポットを横向きに倒して設置し、７５ｒ．ｐ．ｍ．の条件で１５分間回転させる。その後、磁性ポットから、内径２００ｍｍ、深さ４５ｍｍの目開き４５μｍの篩上に微粒状農薬組成物をすべて移し、目開き４５μｍを通過したものの重量（Ａｇ）を測定し、下記式（４）より微粒状農薬組成物の硬度（％）を求める。
<About the hardness of the particulate agricultural chemical composition>
In the present invention, it is important that the hardness of the finely divided agricultural chemical composition is 95 to 100%. When the hardness of the finely divided pesticide composition is less than 95%, when sprayed with a spraying device such as a multi-hose equipped with a power spreader, the finely divided pesticide composition itself is destroyed and pulverized by the impact when spraying the drug. This is because there arises a problem that the scattering property is deteriorated.
In addition, the hardness of the particulate agricultural chemical composition was measured by the following method.
(Hardness measurement method)
A magnetic pot with an inner diameter of 100 mm and an inner depth of 100 mm is charged with 100 g of the finely divided pesticide composition, three magnetic balls (diameter 30 mm, weight 35 g) are added, and then the magnetic pot is covered. On the rotating roller, set the magnetic pot sideways, 75r. p. m. Rotate for 15 minutes under the following conditions. Thereafter, all of the fine pesticide composition was transferred from the magnetic pot onto a sieve having an inner diameter of 200 mm and a depth of 45 mm and having an opening of 45 μm, and the weight (Ag) of the particles having passed through the opening of 45 μm was measured. Determine the hardness (%) of the finely divided pesticide composition.
＜微粒状農薬組成物の調製方法について＞
本発明の微粒状農薬組成物の調製方法は特に限定されないが、例えば次のような方法によって調製できる。
農薬活性成分、結合剤、微粒状担体、必要があればその他の成分を混合機内でよく混合し、適当量の水を添加し更に混練、混合する。その後、必要があれば乾燥、篩分けし微粒状農薬組成物を得ることができる。なお、農薬活性成分は、予めジェット粉砕や湿式粉砕などで微粒子化したものを用いても良く、結合剤は粉体のまま添加しても、予め水に溶解したものを添加してもかまわない。また、流動層内で微粒状担体を流動させながら、農薬活性成分、結合剤、必要があればその他の成分を混合したスラリーを吹きつけて調製しても良く、農薬活性成分、結合剤、微粒状担体、必要があればその他の成分をよく混合し加水後、スクリーン径０．３〜３．０ｍｍ程度のバスケット型押し出し造粒機にて造粒し乾燥したものを、ハンマーミルなどで破砕して微粒状農薬組成物を得る方法などもある。
<About the preparation method of a fine-grained agricultural chemical composition>
Although the preparation method of the fine-grained agricultural chemical composition of this invention is not specifically limited, For example, it can prepare by the following methods.
Agrochemical active ingredients, binders, finely divided carriers, and other ingredients, if necessary, are mixed well in a mixer, and an appropriate amount of water is added, followed by kneading and mixing. Thereafter, if necessary, it can be dried and sieved to obtain a finely divided pesticide composition. In addition, the agrochemical active ingredient may use what was micronized by jet pulverization or wet pulverization in advance, and the binder may be added as a powder or may be added previously dissolved in water. . Alternatively, it may be prepared by spraying a slurry mixed with an agrochemical active ingredient, a binder, and if necessary, other ingredients while fluidizing a particulate carrier in a fluidized bed. If necessary, mix well with other ingredients if necessary, add water, granulate with a basket-type extrusion granulator with a screen diameter of about 0.3 to 3.0 mm, and crush it with a hammer mill. There is also a method for obtaining a finely divided pesticide composition.
＜微粒状農薬組成物の使用態様について＞
上記により調製した微粒状農薬組成物の使用方法は、例えば、動力散布機を装着した多口ホースや直噴管などを用いて作物に散布したり、航空機や有人ヘリコプター、ラジコンヘリコプターなどを用いて空中から作物に散布したり、手や人力散布機で作物に散布したりすることができる他、作物の植え穴や株元に処理したり、土壌混和や土壌表面に処理したり、育苗箱に処理したりすることができる。また、２種以上の微粒状農薬組成物を予め混合した後、散布してもなんら問題ない。なお、本発明の微粒状農薬組成物は、薬剤散布時、散布機による強い衝撃を受けても飛散性に特に大きな影響を受けないことから、衝撃が比較的強い動力散布機を装着した多口ホースや直噴管による散布方法が特に適する。また、多口ホースや直噴管を用いて水田に散布する場合の微粒状農薬組成物の１０アール当たりの施用量は、通常０．５〜５ｋｇであり、好ましくは１〜４ｋｇである。
<About the usage mode of the fine-grained agricultural chemical composition>
The method of using the finely divided pesticide composition prepared as described above is, for example, sprayed on crops using a multi-hose or direct injection pipe equipped with a power spreader, or using an aircraft, a manned helicopter, a radio control helicopter, etc. It can be sprayed on the crops from the air, or can be sprayed on the crops by hand or manpower spreader. Can be processed. Moreover, there is no problem even if two or more kinds of finely divided pesticide compositions are mixed in advance and then sprayed. In addition, the fine granular pesticide composition of the present invention is not particularly affected by the scattering property even when subjected to a strong impact by the spreader when spraying the drug. A spraying method using a hose or a direct injection tube is particularly suitable. Moreover, the application amount per 10 ares of a fine-grained agricultural chemical composition when spraying to a paddy field using a multi-mouth hose or a direct injection tube is usually 0.5 to 5 kg, preferably 1 to 4 kg.
以下、実施例に基づいて本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
なお、以下の実施例、比較例において「部」は、「重量部」の意味である。
［実施例１］
ＭＥＰ（有機リン系殺虫剤） ３部をホワイトカーボン３部に吸油させ、よく混合した後、粒度分布３００μｍ〜４５μｍの微粒状の珪砂９１部、ブドウ糖当量８のデキストリン３部をニーダー内に添加し混合する。この混合物に水６部を添加して更に混合した後、取り出し、流動層乾燥機に添加して乾燥する。その後、目開き３００μｍと６３μｍの篩を用いて篩分けして、本発明の微粒状農薬組成物を得た。なお、得られた微粒状農薬組成物は、３００μｍ〜６３μｍに９９重量％、６３μｍ以下に１重量％の粒度分布で、見掛け比重は１．３、硬度は９８％であった。
EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
In the following examples and comparative examples, “part” means “part by weight”.
[Example 1]
After 3 parts of MEP (Organic Phosphorus Insecticide) were absorbed into 3 parts of white carbon and mixed well, 91 parts of fine silica sand with a particle size distribution of 300 μm to 45 μm and 3 parts of dextrin with 8 glucose equivalents were added to the kneader. Mix. After adding 6 parts of water to this mixture and further mixing, it is taken out and added to a fluid bed dryer and dried. Thereafter, sieving was performed using a sieve having openings of 300 μm and 63 μm to obtain a finely divided agricultural chemical composition of the present invention. The obtained fine granular agricultural chemical composition had a particle size distribution of 99% by weight from 300 to 63 μm and 1% by weight below 63 μm, an apparent specific gravity of 1.3, and a hardness of 98%.
［実施例２］
実施例１の粒度分布３００μｍ〜４５μｍの微粒状の珪砂９１部を、粒度分布３００μｍ〜４５μｍの微粒状の炭酸カルシウム９１部におきかえて、実施例１に準じて調製した。得られた微粒状農薬組成物は、３００μｍ〜６３μｍに９８重量％、６３μｍ以下に２重量％の粒度分布で、見掛け比重は１．２、硬度は９５．５％であった。
［実施例３］
実施例１のホワイトカーボン３部を珪藻土２部にし、粒度分布３００μｍ〜４５μｍの微粒状の珪砂９１部を粒度分布３００μｍ〜４５μｍの微粒状のゼオライト９３部にし、ブドウ糖当量８のデキストリン３部をブドウ糖当量５のデキストリン２部におきかえて、実施例１に準じて調製した。得られた微粒状農薬組成物は、３００μｍ〜６３μｍに９９重量％、６３μｍ以下に１重量％の粒度分布で、見掛け比重は１．１、硬度は９７％であった。
［実施例４］
実施例１の粒度分布３００μｍ〜４５μｍの微粒状の珪砂９１部を８９部にし、ブドウ糖当量８のデキストリン３部をブドウ糖当量１８のデキストリン５部におきかえて、実施例１に準じて調製した。得られた微粒状農薬組成物は、３００μｍ〜６３μｍに９８重量％、６３μｍ以下に２重量％の粒度分布で、見掛け比重は１．３、硬度は９７％であった。
[Example 2]
91 parts of finely divided silica sand having a particle size distribution of 300 μm to 45 μm in Example 1 was replaced with 91 parts of finely divided calcium carbonate having a particle size distribution of 300 μm to 45 μm, and prepared according to Example 1. The resulting finely divided pesticide composition had a particle size distribution of 98% by weight from 300 μm to 63 μm and 2% by weight below 63 μm, an apparent specific gravity of 1.2, and a hardness of 95.5%.
[Example 3]
3 parts of white carbon of Example 1 is made 2 parts of diatomaceous earth, 91 parts of finely divided silica sand having a particle size distribution of 300 μm to 45 μm is made 93 parts of finely divided zeolite having a particle size distribution of 300 μm to 45 μm, and 3 parts of dextrin having a glucose equivalent of 8 is glucose. It was prepared according to Example 1, replacing 2 parts of dextrin with an equivalent weight of 5. The resulting finely divided pesticide composition had a particle size distribution of 99% by weight from 300 μm to 63 μm, 1% by weight below 63 μm, an apparent specific gravity of 1.1, and a hardness of 97%.
[Example 4]
It was prepared in the same manner as in Example 1, except that 91 parts of finely divided silica sand having a particle size distribution of 300 μm to 45 μm in Example 1 was changed to 89 parts, and 3 parts of dextrin having a glucose equivalent of 8 was replaced with 5 parts of dextrin having a glucose equivalent of 18. The resulting finely divided pesticide composition had a particle size distribution of 98% by weight from 300 μm to 63 μm, 2% by weight below 63 μm, an apparent specific gravity of 1.3, and a hardness of 97%.
［実施例５］
カスガマイシン（抗生物質系殺菌剤） ０．１部、ＰＡＰ（イソプロピルアシッドホスフェート）０．１部、粒度分布３００μｍ〜４５μｍの微粒状の珪砂９９．３部、ブドウ糖当量１４のデキストリン０．５部をレーディゲミキサー内に添加する。この混合物に水１部を添加してよく混合した後、取り出し、流動層乾燥機に添加して乾燥する。その後、目開き３００μｍと６３μｍの篩を用いて篩分けして、本発明の微粒状組成物を得た。なお、得られた微粒状農薬組成物は、３００μｍ〜６３μｍに９９．５重量％、６３μｍ以下に０．５重量％の粒度分布で、見掛け比重は１．５、硬度は９９％であった。
[Example 5]
0.1 parts of kasugamycin (antibiotic antibiotic), 0.1 parts of PAP (isopropyl acid phosphate), 99.3 parts of fine silica sand with a particle size distribution of 300 μm to 45 μm, and 0.5 parts of dextrin with 14 glucose equivalents Add to Digger mixer. After adding 1 part of water to this mixture and mixing well, it is taken out and added to a fluid bed dryer and dried. Thereafter, sieving was performed using a sieve having openings of 300 μm and 63 μm to obtain a finely divided composition of the present invention. The resulting finely divided pesticide composition had a particle size distribution of 99.5% by weight from 300 μm to 63 μm, 0.5% by weight below 63 μm, an apparent specific gravity of 1.5, and a hardness of 99%.
［実施例６］
実施例５の粒度分布３００μｍ〜４５μｍの微粒状の珪砂９９．３部を９９．６部にし、ブドウ糖当量１４のデキストリン０．５部を０．２部におきかえて、実施例５に準じて調製した。得られた微粒状農薬組成物は、３００μｍ〜６３μｍに９２重量％、６３μｍ以下に８重量％の粒度分布で、見掛け比重は１．５、硬度は９８％であった。
［実施例７］
実施例５の粒度分布３００μｍ〜４５μｍの微粒状の珪砂９９．３部を９９．７部にし、ブドウ糖当量１４のデキストリン０．５部をポリエチレンオキシド０．１部におきかえて、実施例５に準じて調製した。得られた微粒状農薬組成物は、３００μｍ〜６３μｍに９７重量％、６３μｍ以下に３重量％の粒度分布で、見掛け比重は１．５、硬度は９８％であった。
［実施例８］
実施例５のＰＡＰ０．１部をリン酸０．１部にし、粒度分布３００μｍ〜４５μｍの微粒状の珪砂９９．３部を粒度分布３００μｍ〜４５μｍの微粒状の軽石９９．６部にし、ブドウ糖当量１４のデキストリン０．５部をアラビアガム０．２部におきかえて、実施例５に準じて調製した。得られた微粒状農薬組成物は、３００μｍ〜６３μｍに９９重量％、６３μｍ以下に１重量％の粒度分布で、見掛け比重は１．１、硬度は９６％であった。
[Example 6]
Prepared according to Example 5, replacing 99.3 parts of finely divided silica sand with a particle size distribution of 300 μm to 45 μm of Example 5 by 99.6 parts and 0.5 part of dextrin having a glucose equivalent of 14 by 0.2 parts. did. The resulting finely divided pesticide composition had a particle size distribution of 92% by weight from 300 μm to 63 μm and 8% by weight below 63 μm, an apparent specific gravity of 1.5, and a hardness of 98%.
[Example 7]
According to Example 5, except that 99.3 parts of finely divided silica sand having a particle size distribution of 300 μm to 45 μm in Example 5 was changed to 99.7 parts and 0.5 part of dextrin having a glucose equivalent of 14 was replaced with 0.1 parts of polyethylene oxide. Prepared. The resulting finely divided pesticide composition had a particle size distribution of 97% by weight from 300 to 63 μm and 3% by weight below 63 μm, an apparent specific gravity of 1.5, and a hardness of 98%.
[Example 8]
0.1 part of PAP of Example 5 was changed to 0.1 part of phosphoric acid, 99.3 parts of finely divided silica sand having a particle size distribution of 300 μm to 45 μm were changed to 99.6 parts of finely divided pumice having a particle size distribution of 300 μm to 45 μm, and glucose equivalent 14 parts of dextrin was replaced with 0.2 part of gum arabic and prepared according to Example 5. The resulting finely divided pesticide composition had a particle size distribution of 99% by weight from 300 μm to 63 μm, 1% by weight below 63 μm, an apparent specific gravity of 1.1, and a hardness of 96%.
［実施例９］
フルトラニル（酸アミド系殺菌剤）２部、粒度分布３００μｍ〜４５μｍの微粒状の珪砂９７部、ブドウ糖当量１８のデキストリン１部をニーダー内に添加する。この混合物に水１．５部を添加してよく混合した後、取り出し、流動層乾燥機に添加して乾燥する。その後、目開き３００μｍと６３μｍの篩を用いて篩分けして、本発明の微粒状農薬組成物を得た。なお、得られた微粒状農薬組成物は、３００μｍ〜６３μｍに９８．５重量％、６３μｍ以下に１．５重量％の粒度分布で、見掛け比重は１．４、硬度は９９％であった。
［実施例１０］
実施例９の粒度分布３００μｍ〜４５μｍの微粒状の珪砂９７部を９７．２部にし、ブドウ糖当量１８のデキストリン１部をブドウ糖当量９のデキストリン０．８部におきかえて、実施例９に準じて調製した。得られた微粒状農薬組成物は、３００μｍ〜６３μｍに９９重量％、６３μｍ以下に１重量％の粒度分布で、見掛け比重は１．４、硬度は９９％であった。
[Example 9]
2 parts of flutolanil (acid amide fungicide), 97 parts of finely divided silica sand having a particle size distribution of 300 μm to 45 μm, and 1 part of dextrin having a glucose equivalent of 18 are added to the kneader. After adding 1.5 parts of water to this mixture and mixing well, it is taken out and added to a fluid bed dryer and dried. Thereafter, sieving was performed using a sieve having openings of 300 μm and 63 μm to obtain a finely divided agricultural chemical composition of the present invention. The resulting finely divided pesticide composition had a particle size distribution of 98.5% by weight from 300 μm to 63 μm and 1.5% by weight below 63 μm, an apparent specific gravity of 1.4, and a hardness of 99%.
[Example 10]
According to Example 9, except that 97 parts of finely divided silica sand having a particle size distribution of 300 μm to 45 μm in Example 9 was changed to 97.2 parts, and 1 part of dextrin having a glucose equivalent of 18 was replaced with 0.8 part of dextrin having a glucose equivalent of 9. Prepared. The resulting finely divided pesticide composition had a particle size distribution of 99% by weight from 300 μm to 63 μm, 1% by weight below 63 μm, an apparent specific gravity of 1.4, and a hardness of 99%.
［比較例１］
実施例１の粒度分布３００μｍ〜４５μｍの微粒状の珪砂９１部を９３．５部にし、ブドウ糖当量８のデキストリン３部を０．５部におきかえて、目開き３００μｍと４５μｍの篩を用いて篩分けした以外は、実施例１に準じて調製した。得られた微粒状農薬組成物は、３００μｍ〜６３μｍに８８重量％、６３μｍ以下に１２重量％の粒度分布で、見掛け比重は１．３、硬度は９５％であった。
［比較例２］
実施例２の粒度分布３００μｍ〜４５μｍの微粒状の炭酸カルシウム９１部を９３部にし、ブドウ糖当量８のデキストリン３部を１部におきかえて、実施例２に準じて調製した。得られた微粒状農薬組成物は、３００μｍ〜６３μｍに９１重量％、６３μｍ以下に９重量％の粒度分布で、見掛け比重は１．２、硬度は９３％であった。
［比較例３］
実施例１のホワイトカーボン３部を７部にし、粒度分布３００μｍ〜４５μｍの微粒状の珪砂９１部を８６部にし、ブドウ糖当量８のデキストリン３部を４部におきかえて、実施例１に準じて調製した。得られた微粒状農薬組成物は、３００μｍ〜６３μｍに９７重量％、６３μｍ以下に３重量％の粒度分布で、見掛け比重は０．９、硬度は９６％であった。
［比較例４］
実施例３の珪藻土２部をホワイトカーボン２部におきかえて、実施例３に準じて調製した。得られた微粒状農薬組成物は、３００μｍ〜６３μｍに９８重量％、６３μｍ以下に２重量％の粒度分布で、見掛け比重は０．９、硬度は９７％であった。
[Comparative Example 1]
In Example 1, 91 parts of finely divided silica sand having a particle size distribution of 300 μm to 45 μm are changed to 93.5 parts, 3 parts of dextrin having a glucose equivalent of 8 is replaced with 0.5 parts, and sieves with openings of 300 μm and 45 μm are used. It prepared according to Example 1 except having divided. The resulting finely divided pesticide composition had a particle size distribution of 88% by weight from 300 μm to 63 μm, 12% by weight below 63 μm, an apparent specific gravity of 1.3, and a hardness of 95%.
[Comparative Example 2]
It was prepared in the same manner as in Example 2, except that 91 parts of finely divided calcium carbonate having a particle size distribution of 300 μm to 45 μm in Example 2 was replaced with 93 parts and 3 parts of dextrin having a glucose equivalent of 8 was replaced with 1 part. The resulting finely divided pesticide composition had a particle size distribution of 91% by weight from 300 to 63 μm, 9% by weight below 63 μm, an apparent specific gravity of 1.2, and a hardness of 93%.
[Comparative Example 3]
According to Example 1, except that 3 parts of white carbon in Example 1 are changed to 7 parts, 91 parts of finely divided silica sand having a particle size distribution of 300 μm to 45 μm are changed to 86 parts, and 3 parts of dextrin having a glucose equivalent of 8 are changed to 4 parts. Prepared. The resulting finely divided pesticide composition had a particle size distribution of 97% by weight from 300 to 63 μm and 3% by weight below 63 μm, an apparent specific gravity of 0.9, and a hardness of 96%.
[Comparative Example 4]
It was prepared according to Example 3 by replacing 2 parts of diatomaceous earth of Example 3 with 2 parts of white carbon. The resulting finely divided pesticide composition had a particle size distribution of 98% by weight from 300 μm to 63 μm and 2% by weight below 63 μm, an apparent specific gravity of 0.9, and a hardness of 97%.
［比較例５］
実施例５のブドウ糖当量１４のデキストリンを除き、粒度分布３００μｍ〜４５μｍの微粒状の珪砂９９．３部を９９．８部におきかえて、実施例５に準じて調製した。得られた微粒状農薬組成物は、３００μｍ〜６３μｍに９９重量％、６３μｍ以下に１重量％の粒度分布で、見掛け比重は１．５、硬度は９９％であった。
［比較例６］
実施例５の粒度分布３００μｍ〜４５μｍの微粒状の珪砂９９．３部を粒度分布１５０μｍ〜４５μｍの微粒状の珪砂９９．７部にし、ブドウ糖当量１４のデキストリン０．５部を０．１部におきかえて、目開き３００μｍと４５μm の篩を用いて篩分けした以外は、実施例５に準じて調製した。得られた微粒状農薬組成物は、３００μｍ〜６３μｍに８６重量％、６３μｍ以下に１４重量％の粒度分布で、見掛け比重は１．５、硬度は９８％であった。
［比較例７］
実施例５の粒度分布３００μｍ〜４５μｍの微粒状の珪砂９９．３部を粒度分布４２５μｍ〜３００μｍの微粒状の珪砂９９．３部におきかえて、目開き５００μｍと３００μｍの篩を用いて篩分けした以外は、実施例５に準じて調製した。得られた微粒状農薬組成物は、３００μｍ以上に１００重量％の粒度分布で、見掛け比重は１．６、硬度は９９％であった。
[Comparative Example 5]
Except for dextrin having a glucose equivalent of 14 in Example 5, 99.3 parts of finely divided silica sand having a particle size distribution of 300 μm to 45 μm were replaced with 99.8 parts and prepared according to Example 5. The resulting finely divided pesticide composition had a particle size distribution of 99% by weight from 300 μm to 63 μm, 1% by weight below 63 μm, an apparent specific gravity of 1.5, and a hardness of 99%.
[Comparative Example 6]
In Example 5, 99.3 parts of finely divided silica sand having a particle size distribution of 300 μm to 45 μm was changed to 99.7 parts of finely divided silica sand having a particle size distribution of 150 μm to 45 μm, and 0.5 part of dextrin having a glucose equivalent of 14 was changed to 0.1 part. It was prepared according to Example 5 except that the sieving was performed using a sieve having openings of 300 μm and 45 μm. The resulting finely divided pesticide composition had a particle size distribution of 86% by weight from 300 to 63 μm, 14% by weight below 63 μm, an apparent specific gravity of 1.5, and a hardness of 98%.
[Comparative Example 7]
The fine-grained silica sand 99.3 parts of Example 5 having a particle size distribution of 300 μm to 45 μm was replaced with 99.3 parts of fine-grained silica sand having a particle size distribution of 425 μm to 300 μm, and sieved using a sieve having openings of 500 μm and 300 μm. Except for the above, it was prepared according to Example 5. The resulting finely divided pesticide composition had a particle size distribution of 100% by weight over 300 μm, an apparent specific gravity of 1.6, and a hardness of 99%.
［比較例８］
実施例９の粒度分布３００μｍ〜４５μｍの微粒状の珪砂９７部を粒度分布１５０μｍ〜４５μｍｍの微粒状の珪砂９７．２部にし、ブドウ糖当量１８のデキストリン１部をリグニンスルホン酸ナトリウム０．８部におきかえて、目開き３００μｍと４５μｍの篩を用いて篩分けした以外は、実施例９に準じて調製した。得られた微粒状農薬組成物は、３００μｍ〜６３μｍに８８重量％、６３μｍ以下に１２重量％の粒度分布で、見掛け比重は１．４、硬度は９８％であった。
［比較例９］
実施例１０の粒度分布３００μｍ〜４５μｍの微粒状の珪砂９７．２部を粒度分布１５０μｍ〜４５μｍの微粒状の珪砂９７．２部におきかえて、目開き３００μｍと４５μｍの篩を用いて篩分けした以外は、実施例１０に準じて調製した。得られた微粒状農薬組成物は３００μｍ〜６３μｍに８５重量％、６３μｍ以下に１５重量％の粒度分布で、見掛け比重は１．４、硬度は９７％であった。
[Comparative Example 8]
In Example 9, 97 parts of finely divided silica sand having a particle size distribution of 300 μm to 45 μm was changed to 97.2 parts of finely divided silica sand having a particle size distribution of 150 μm to 45 μm, and 1 part of dextrin having a glucose equivalent of 18 was changed to 0.8 part of sodium lignin sulfonate. It was prepared according to Example 9 except that the sieving was performed using a sieve having openings of 300 μm and 45 μm. The resulting finely divided pesticide composition had a particle size distribution of 88% by weight from 300 μm to 63 μm, 12% by weight below 63 μm, an apparent specific gravity of 1.4, and a hardness of 98%.
[Comparative Example 9]
97.2 parts of fine silica sand having a particle size distribution of 300 μm to 45 μm in Example 10 was replaced with 97.2 parts of fine silica sand having a particle size distribution of 150 μm to 45 μm, and sieved using a sieve having openings of 300 μm and 45 μm. Except for the above, it was prepared according to Example 10. The resulting finely divided pesticide composition had a particle size distribution of 85% by weight from 300 μm to 63 μm, 15% by weight below 63 μm, an apparent specific gravity of 1.4, and a hardness of 97%.
［比較例１０］
ＭＥＰ３部をホワイトカーボン３部に吸油させ、その後、粒度分布４５μｍ以下の粉状のクレー９４部を加え、ハンマーミルにて混合し、ＭＥＰ粉剤を得た。
［比較例１１］
カスガマイシン０．１部、ＰＡＰ０．１部、粒度分布４５μｍ以下の粉状のクレー９９．８部をハンマーミルにて混合し、カスガマイシン粉剤を得た。
［比較例１２］
フルトラニル２部、ホワイトカーボン１部、粒度分布４５μｍ以下の粉状のクレー９７部をハンマーミルにて混合し、フルトラニル粉剤を得た。
[Comparative Example 10]
3 parts of MEP was absorbed into 3 parts of white carbon, and then 94 parts of powdery clay having a particle size distribution of 45 μm or less was added and mixed with a hammer mill to obtain an MEP powder.
[Comparative Example 11]
Kasugamycin powder was obtained by mixing 0.1 part of kasugamycin, 0.1 part of PAP and 99.8 parts of powdery clay having a particle size distribution of 45 μm or less with a hammer mill.
[Comparative Example 12]
2 parts of flutolanil, 1 part of white carbon, and 97 parts of powdery clay having a particle size distribution of 45 μm or less were mixed with a hammer mill to obtain a flutolanil powder.
次に、試験例により、本発明の微粒状農薬組成物の有用性を示す。
［試験例１］飛散性試験
ビニールハウス内に、動力散布機を装着した２０ｍの多口ホースを設置する（地上からの高さが１ｍとなるようにホースを設置）。次に、多口ホースの中心部（動力散布機から１０ｍの位置）の後方２ｍに工場扇を設置し、多口ホース中心部の風速が２ｍ／秒となるように工場扇を稼動させる。また、多口ホース中心部の前方１０ｍの位置にポールを立て、ポールの高さ１．５ｍ位置にシャーレ（直径９ｃｍ）を設置する。その後、多口ホースから実施例および比較例に準じて調製した微粒状農薬組成物を１ｋｇ散布し、シャーレに回収された農薬有効成分量を測定した。なお、実施例１〜実施例４および比較例１〜比較例４については、比較例１０（ＭＥＰ（３％）粉剤）のＭＥＰ回収量との比較（ＭＥＰ（３％）粉剤のシャーレに回収されたＭＥＰ量を１００とした時の割合）から飛散率（％）を求めた。また、同様に、実施例５〜実施例８および比較例５〜比較例７については、比較例１１のカスガマイシン（０．１％）粉剤を散布した場合との比較で飛散率（％）を求めた。また、実施例９、実施例１０、比較例８および比較例９については、比較例１２のフルトラニル（２％）粉剤を散布した場合との比較で飛散率（％）を求めた。
その試験結果を表１（実施例）および表2（比較例）に示す。
Next, the usefulness of the particulate agricultural chemical composition of the present invention will be shown by test examples.
[Test Example 1] Scatterability test A 20-m multi-hose equipped with a power spreader is installed in a greenhouse (installed so that the height from the ground is 1 m). Next, a factory fan is installed 2 m behind the center of the multi-nose hose (position 10 m from the power spreader), and the factory fan is operated so that the wind speed at the center of the multi-nose hose is 2 m / sec. A pole is set up at a position 10 m ahead of the center of the multi-hose hose, and a petri dish (diameter 9 cm) is installed at a position 1.5 m in height of the pole. Thereafter, 1 kg of a finely divided pesticide composition prepared according to the examples and comparative examples from a multi-hose was sprayed, and the amount of active agricultural chemical components collected in the petri dish was measured. In addition, about Example 1- Example 4 and Comparative Example 1- Comparative Example 4, it compares with the MEP collection amount of the comparative example 10 (MEP (3%) powder), and is collect | recovered in the petri dish of MEP (3%) powder. Further, the scattering rate (%) was determined from the ratio of the MEP amount to 100). Similarly, for Examples 5 to 8 and Comparative Examples 5 to 7, the scattering rate (%) is obtained by comparison with the case of spraying the kasugamycin (0.1%) powder of Comparative Example 11. It was. Moreover, about Example 9, Example 10, the comparative example 8, and the comparative example 9, the scattering rate (%) was calculated | required by the comparison with the case where the flutolanil (2%) powder agent of the comparative example 12 was sprayed.
The test results are shown in Table 1 (Examples) and Table 2 (Comparative Examples).
［試験例２］有効成分の剥離試験
ビニールハウス内に、動力散布機を装着した２０ｍの多口ホースを設置する（地上からの高さが１ｍとなるようにホースを設置）。多口ホースの下（動力散布機から１、４、７、１０、１３、１６、１９ｍの位置）にプラスチック製容器（縦１ｍ×
横０．５ｍ × 高さ０．４ｍ）を設置し、多口ホースから実施例および比較例に準じて調製した微粒状農薬組成物を１ｋｇ散布した。散布後、プラスチック製容器内の微粒状農薬組成物を回収し全量を均一に混合し、下記式（５）から有効成分の剥離率（％）を求めた。その試験結果を表１（実施例）および表2（比較例）に示す。
なお、散布の衝撃によって剥離した有効成分、あるいは微粒状農薬組成物の硬度が弱いために発生した微粉などは粉立ちし、プラスチック容器内にほとんど回収されていないことが肉眼で観察された。
[Test Example 2] Peeling test of active ingredient A 20-m multi-nose hose equipped with a power spreader is installed in a greenhouse (installed so that the height from the ground is 1 m). A plastic container (vertical 1 m x length) under the multi-hose (positions 1, 4, 7, 10, 13, 16, 19 m from the power spreader)
A horizontal pesticide composition prepared according to Examples and Comparative Examples from a multi-hose was sprayed. After spraying, the finely divided pesticide composition in the plastic container was collected and the whole amount was mixed uniformly, and the peel rate (%) of the active ingredient was determined from the following formula (5). The test results are shown in Table 1 (Examples) and Table 2 (Comparative Examples).
In addition, it was observed with the naked eye that the active ingredient peeled by the impact of spraying or the fine powder generated due to the weak hardness of the fine-grained agricultural chemical composition was powdered and hardly collected in the plastic container.
［試験例３］付着性試験
ビニールで作成した囲い（３ｍ×３ｍ）の中に、８葉期の水稲８株が移植されているプラスチック製容器（０．５ｍ×２ｍ）を設置し、その上部１ｍの高さから、囲いの中に均一に手動式散布機（ミゼットダスター）を用いて、実施例および比較例に準じて調製した微粒状農薬組成物を２７ｇ（３ｋｇ／１０アール相当）散布する。５分経過後、水稲８株の地上部を切り取り、地上部に付着していた有効成分量を測定した。なお、実施例１〜実施例４および比較例１〜比較例４については、比較例１０（ＭＥＰ（３％）粉剤）のＭＥＰ量との比較（ＭＥＰ（３％）粉剤のＭＥＰ付着量を１００とした時の割合）から付着率（％）を求めた。また、同様に、実施例５〜実施例８および比較例５〜比較例７については、比較例１１のカスガマイシン（０．１％）粉剤を散布した場合との比較で付着率（％）を求めた。また、実施例９、実施例１０、比較例８および比較例９については、比較例１２のフルトラニル（２％）粉剤を散布した場合との比較で付着率（％）を求めた。
その試験結果を表１（実施例）および表2（比較例）に示す。
[Test Example 3] Adhesion test A plastic container (0.5m x 2m) in which 8 rice plants of 8 leaf stages are transplanted is placed in an enclosure made of vinyl (3m x 3m), and the upper part From a height of 1 m, 27 g (equivalent to 3 kg / 10 are) of finely divided pesticide composition prepared according to the examples and comparative examples is sprayed uniformly in the enclosure using a manual sprayer (midget duster). . After the elapse of 5 minutes, the above-ground part of 8 paddy rice plants was cut out, and the amount of the active ingredient adhering to the above-ground part was measured. In addition, about Example 1- Example 4 and Comparative Example 1- Comparative Example 4, it compares with the MEP amount of Comparative Example 10 (MEP (3%) powder) (MEP adhesion amount of MEP (3%) powder is set to 100. The ratio (%) was determined from the ratio). Similarly, for Examples 5 to 8 and Comparative Examples 5 to 7, the adhesion rate (%) is obtained by comparison with the case of spraying the kasugamycin (0.1%) powder of Comparative Example 11. It was. Moreover, about Example 9, Example 10, the comparative example 8, and the comparative example 9, the adhesion rate (%) was calculated | required by the comparison with the case where the flutolanil (2%) powder agent of the comparative example 12 was sprayed.
The test results are shown in Table 1 (Examples) and Table 2 (Comparative Examples).
表１に記載された試験結果から明らかなように、実施例１〜実施例１０の飛散率は０．３〜６．９％であり、付着率は７７〜９１％であった。一方、表２に示された試験結果から明らかなように、９０重量％以上の粒子が粒度分布３００μｍ〜６３μｍの範囲以外にあり、６３μｍ以下の粒子が１０％より多く含む比較例１、比較例６、比較例８および比較例９の飛散率は１０．９〜１６．６％と高い値となり、３００μｍ以上の粒子からなる比較例７の付着率は２６％と低い値となった。また、硬度が９５％未満である比較例２の飛散率は１３．８％と高い値となり、見掛け比重が１．０未満である比較例３および比較例４の飛散率は１０．７〜１１．７％と高い値となった。そして、結合剤を含有しない比較例５の飛散率は３８．２％と高い値となった。 As is clear from the test results described in Table 1, the scattering rate of Examples 1 to 10 was 0.3 to 6.9%, and the adhesion rate was 77 to 91%. On the other hand, as is apparent from the test results shown in Table 2, Comparative Example 1 and Comparative Example in which 90% by weight or more of the particles are outside the range of particle size distribution of 300 μm to 63 μm and 63 μm or less of the particles are more than 10% 6, the scattering rate of Comparative Example 8 and Comparative Example 9 was as high as 10.9 to 16.6%, and the adhesion rate of Comparative Example 7 consisting of particles of 300 μm or more was as low as 26%. Further, the scattering rate of Comparative Example 2 having a hardness of less than 95% is as high as 13.8%, and the scattering rates of Comparative Example 3 and Comparative Example 4 having an apparent specific gravity of less than 1.0 are 10.7 to 11. The value was as high as 7%. And the scattering rate of the comparative example 5 which does not contain a binder was a high value of 38.2%.
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