JP2005162739A - Agrochemical-containing fine particle and method for producing the same - Google Patents
Agrochemical-containing fine particle and method for producing the same Download PDFInfo
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Abstract
Description
本発明は、農薬含有微粒子及びその製造方法に関する。 The present invention relates to agrochemical-containing fine particles and a method for producing the same.
従来、薬効の持続、薬害の軽減等を目的として、農薬活性成分を徐放化した徐放性農薬製剤が、各種提案されている。このような徐放性農薬製剤としては、農薬活性成分をマイクロカプセル化したもの（例えば、特許文献１参照）、農薬活性成分を含有する粒子を被覆したもの（例えば、特許文献２参照）等が知られている。 Conventionally, various sustained-release agrochemical formulations in which an agrochemical active ingredient is sustained-released have been proposed for the purpose of sustaining drug efficacy and reducing phytotoxicity. Examples of such sustained-release agrochemical formulations include microencapsulated agrochemical active ingredients (see, for example, Patent Document 1), those coated with particles containing agrochemical active ingredients (for example, see Patent Document 2), and the like. Are known.
本発明は、優れた特性を有する農薬徐放性の農薬含有微粒子及びその製造方法を提供することを課題とする。 An object of the present invention is to provide an agrochemical sustained-release agrochemical-containing fine particle having excellent characteristics and a method for producing the same.
本発明者等は鋭意検討を行い、水難溶性農薬活性成分と酸化ポリエチレンとを水に分散させた分散液を噴霧乾燥して得られる微粒子が、該水難溶性農薬活性成分を徐放化すると共に、水に懸濁させた場合の分散状態の持続性が優れたものであることを見出し、本発明を完成させた。
即ち、本発明は、水難溶性農薬活性成分と酸化ポリエチレンとを水に分散させた分散液を噴霧乾燥して得られる農薬含有微粒子；及び水難溶性農薬活性成分と酸化ポリエチレンとを水に分散させた分散液を、噴霧乾燥することを特徴とする農薬含有微粒子の製造方法を提供する。
The inventors of the present invention diligently studied, fine particles obtained by spray-drying a dispersion obtained by dispersing a water-insoluble pesticide active ingredient and polyethylene oxide in water, gradually release the water-insoluble pesticide active ingredient, The present invention was completed by finding that the sustainability of the dispersed state when suspended in water was excellent.
That is, the present invention is a method comprising spray-drying a dispersion in which a poorly water-soluble pesticidal active ingredient and polyethylene oxide are dispersed in water; and a poorly water-soluble pesticidal active ingredient and polyethylene oxide dispersed in water. Disclosed is a method for producing agrochemical-containing fine particles, wherein the dispersion is spray-dried.
本発明の農薬含有微粒子は、農薬活性成分を徐放化すると共に水に懸濁させた場合の分散状態の持続性が良好である。 The agrochemical-containing fine particles of the present invention have good dispersion state sustainability when the agrochemical active ingredient is sustainedly released and suspended in water.
本発明の農薬含有微粒子は、水難溶性農薬活性成分と酸化ポリエチレンとを水に分散させた分散液を、噴霧乾燥して得られるものである。 The agrochemical-containing fine particles of the present invention are obtained by spray-drying a dispersion in which a water-insoluble pesticidal active ingredient and polyethylene oxide are dispersed in water.
本発明に用いられる水難溶性農薬活性成分は、常温（２５℃）において固体でも、液体のでもよいが、本発明の農薬含有微粒子の製造のしやすさの点から融点が８０℃以上のものが好ましい。
また、本発明に用いられる水難溶性農薬活性成分とは、２５℃における水溶解性が通常１０００ｍｇ／１０００ｍｌ以下の農薬活性成分をいい、好ましくは２５℃における水溶解性が１００ｍｇ／１０００ｍｌ以下の農薬活性成分をいう。
農薬活性成分としては、例えば殺虫活性成分、殺菌活性成分、除草活性成分、及び植物成長調節活性成分が挙げられ、本発明に用いることができる水難溶性農薬活性成分として、具体的には例えば以下の化合物が挙げられる。
The poorly water-soluble pesticidal active ingredient used in the present invention may be solid or liquid at room temperature (25 ° C.), but those having a melting point of 80 ° C. or higher from the viewpoint of ease of production of the pesticide-containing fine particles of the present invention. preferable.
Further, the poorly water-soluble pesticidal active ingredient used in the present invention means an pesticidal active ingredient whose water solubility at 25 ° C. is usually 1000 mg / 1000 ml or less, preferably pesticidal activity whose water solubility at 25 ° C. is 100 mg / 1000 ml or less. Ingredients.
Pesticide active ingredients include, for example, insecticidal active ingredients, bactericidal active ingredients, herbicidal active ingredients, and plant growth regulating active ingredients. Specific examples of poorly water-soluble pesticide active ingredients that can be used in the present invention include the following: Compounds.
殺虫活性成分：シペルメトリン、デルタメトリン、フェンプロパトリン、トラロメトリン、アクリナトリン、ビフェントリン、レスメトリン、テトラメトリン、ペルメトリン、イソプロカルブ、キシリルカルブ、ＸＭＣ、カルバリル、カルボフラン、フェノキシカルブ、アラニカルブ、フェノブカルブ、ベンダイオカルブ、テトラクロルビンホス、ジメチルビンホス、ホサロン、クロルピリホス、クロルピリホスメチル、ピリダフェンチオン、キナルホス、メチダチオン、アジンホスエチル、アジンホスメチル、サリチオン、シアノホス、ＥＰＮ、シアノフェンホス、ジフルベンズロン、クロルフルアズロン、ルフェヌロン、ヘキサフルムロン、フルフェノクスロン、フルシクロクスロン、ジアフェンチウロン、ヘキシチアゾクス、ノヴァルロン、テフルベンズロン、トリフルムロン、ベンスルタップ、フェノキシカルブ、フェナザキン、フェンピロキシメート、ピリダベン、ヒドラメチルノン、チオジカルブ、クロルフェナピル、ピメトロジン、ピリミジフェン、テブフェノジド、テブフェンピラド、トリアザメート、スルフルラミド、ミルベメクチン、ピリダリル等。 Insecticidal active ingredients: cypermethrin, deltamethrin, fenpropatoline, tralomethrin, acrinatrin, bifenthrin, resmethrin, tetramethrin, permethrin, isoprocarb, xylylcarb, XMC, carbaryl, carbofuran, phenoxycarb, alanibcarb, fenodicarb Dimethylvinphos, hosalon, chlorpyrifos, chlorpyrifosmethyl, pyridafenthion, quinalphos, methidathion, azinephosethyl, azinephosmethyl, salicion, cyanophos, EPN, cyanophenphos, diflubenzuron, chlorfluazuron, lufenuron, hexaflumuron, flufenoxuron, full Cycloxuron, diafenthiuron, hexythiazox, Noval Emissions, teflubenzuron, triflumuron, bensultap, fenoxycarb, fenazaquin, fenpyroximate, pyridaben, hydramethylnon, thiodicarb, chlorfenapyr, pymetrozine, pyrimidifen, tebufenozide, tebufenpyrad, triazamate, sulfluramid, milbemectin, pyridalyl, and the like.
殺菌活性成分：ベノミル、カルベンダジム、チオファネートメチル、ジエトフェンカルブ、プロシミドン、イプロジオン、ビンクロゾリン、ジニコナゾール、テブコナゾール、ジフェノコナゾール、シプロコナゾール、フルシラゾール、トリアジメフォン、フラメトピル、メプロニル、フルトラニル、トルクロホスメチル、ピラゾホス、ピリメサニル、メパニピリム、シプロジニル、フルジオキソニル、フェンピクロニル、アゾキシストロビン、クレソキシムメチル、メトミノストロビン、クロロタロニル、マンゼブ、キャプタン、フォルペット、プロベナゾール、ジメトモルフ、ファモキサドン、オキソリニック酸、フルアジナム、フェリムゾン等。 Bactericidal active ingredients: benomyl, carbendazim, thiophanate methyl, dietofencarb, procymidone, iprodione, vinclozoline, diniconazole, tebuconazole, difenoconazole, cyproconazole, flusilazole, triadimephone, framethopyl, mepronil, flutolanil, tolcrofosmethyl, pyrazomepyrames Cyprodinil, fludioxonil, fenpicuronyl, azoxystrobin, cresoxime methyl, metminostrobin, chlorothalonil, manzeb, captan, phorpet, probenazole, dimethomorph, famoxadone, oxolinic acid, fluazinam, ferrimzone and the like.
除草活性成分：フェノキサプロップ−ｐ−エチル、シハロホップブチル、ベンスルフロンメチル、ニコスルフロン、シクロスルファムロン、トリフルスルフロンメチル、イマザキン、フルメツラム、アトラジン、メトリブジン、フルオメツロン、イソプロチュロン、プロパニル、ブロモキシニル、アイオキシニル、ベンタゾン、フルミオキサジン、フルチアセットメチル、アザフェニジン、サルフェントラゾン、ノルフルラゾン、ジフルフェニカン、イソキサフルトール、ペンディメサリン、トリフルラリン、メフェナセット、メコプロップ、フルロキシピル等。 Herbicidal active ingredients: phenoxaprop-p-ethyl, cyhalohop butyl, bensulfuron methyl, nicosulfuron, cyclosulfamuron, triflusulfuron methyl, imazaquin, flumeturum, atrazine, metribuzin, fluometuron, isoproturon, propanil, Bromoxynyl, ioxinyl, bentazone, flumioxazin, fluthiaset methyl, azaphenidine, sulfentrazone, norflurazon, diflufenican, isoxaflutol, pendimesalin, trifluralin, mefenacet, mecoprop, fluroxypyr and the like.
植物成長調節活性成分：チジアズロン、イナベンファイド、パクロブトラゾール 、ウニコナゾール等。 Plant growth regulating active ingredients: thidiazulone, inavenfide, paclobutrazol, uniconazole and the like.
本発明において酸化ポリエチレンとは、一般に“酸化ポリエチレンワックス”とも呼称されている物質（CAS No. 68441-17-8）であって、ポリエチレンを酸化することにより製造される。酸化ポリエチレンの市販品を入手することも可能であり、例えば、ネオワックスＥ（ヤスハラケミカル社製、融点：１００℃、酸価：１５ｍｇＫＯＨ／ｇ）、ネオワックスＥ−２０（ヤスハラケミカル社製、融点：１０２℃、酸価：１８ｍｇＫＯＨ／ｇ）、ネオワックスＥ−３（ヤスハラケミカル社製；融点：１１０℃、酸価：１ｍｇＫＯＨ／ｇ）、Ｌｉｃｏｗａｘ ＰＥＤ ５２２（クラリアント社製、滴点：１０２−１０７℃、酸価：２２−２８ｍｇＫＯＨ／ｇ）、Ｌｉｃｏｌｕｂ Ｈ１２（クラリアント社製、滴点：１００−１０８℃、酸価：１５−１９ｍｇＫＯＨ／ｇ）、Ｃｅｒｉｄｕｓｔ ３７１９（クラリアント社製、滴点：１１３−１１８℃、酸価：１６−１９ｍｇＫＯＨ／ｇ）、Ｌｕｗａｘ ＯＡ２ ｐｏｗｄｅｒ（BOYSAN社製、融点：１０７−１１３℃、酸価：１９−２５ｍｇＫＯＨ／ｇ）、Ｍａｒｃｕｓ Ｍ３４００（Marcus Oil & Chemical社製、融点：１０９℃(peak)、酸価：１２−１６ｍｇＫＯＨ／ｇ）、Ｍａｒｃｕｓ Ｍ３５００（Marcus Oil & Chemical社製、融点：１０９℃(peak)、酸価：２４ｍｇＫＯＨ／ｇ）が挙げられる。本発明においては、１ｇに含まれる遊離カルボン酸を中和するために必要な水酸化カリウムの量（以下、酸価と記す。）が１０〜３０ｍｇである酸化ポリエチレン、融点が８０〜１５０℃の酸化ポリエチレンが好ましい。なお、ここで言う酸化ポリエチレンの融点とは、固体の酸化ポリエチレンを加熱したときに、該酸化ポリエチレンが溶け始める温度をいう。 In the present invention, the oxidized polyethylene is a substance (CAS No. 68441-17-8) generally referred to as “oxidized polyethylene wax” and is produced by oxidizing polyethylene. It is also possible to obtain a commercially available product of oxidized polyethylene. For example, Neowax E (manufactured by Yashara Chemical Co., melting point: 100 ° C., acid value: 15 mgKOH / g), Neowax E-20 (manufactured by Yashara Chemical Co., melting point: 102) ° C, acid value: 18 mgKOH / g), Neowax E-3 (manufactured by Yashara Chemical Co .; melting point: 110 ° C, acid value: 1 mgKOH / g), Licowax PED 522 (manufactured by Clariant, dropping point: 102-107 ° C, acid) Value: 22-28 mg KOH / g), Licolub H12 (manufactured by Clariant, dropping point: 100-108 ° C., acid value: 15-19 mg KOH / g), Ceridust 3719 (manufactured by Clariant, dropping point: 113-118 ° C., acid) Value: 16-19 mg KOH / g), Luwax OA2 powder (manufactured by BOYSAN, melting point) 107-113 ° C., acid value: 19-25 mg KOH / g), Marcus M3400 (manufactured by Marcus Oil & Chemical, melting point: 109 ° C. (peak), acid value: 12-16 mg KOH / g), Marcus M3500 (Marcus Oil & Chemical And a melting point: 109 ° C. (peak), acid value: 24 mgKOH / g). In the present invention, polyethylene oxide having an amount of potassium hydroxide necessary for neutralizing free carboxylic acid contained in 1 g (hereinafter referred to as acid value) of 10 to 30 mg, melting point of 80 to 150 ° C. Oxidized polyethylene is preferred. The melting point of oxidized polyethylene here refers to the temperature at which the oxidized polyethylene starts to melt when the solid oxidized polyethylene is heated.
また、本発明に用いられる酸化ポリエチレンは、例えば、ポリエチレンが水に分散した樹脂エマルジョンを酸素酸化することにより、酸化ポリエチレンが分散した樹脂エマルジョンとして製造することもできるし、酸化ポリエチレンが分散した樹脂エマルジョンの市販品を入手することも可能であり、例えば、Ａｇｒｏｃｅｒ ＤＣＸ １６８８（クラリアント社製、固形分量：約１８％）、Ｐｏｌｉｇｅｎ ＷＥ６（BOYSAN社製、固形分量：３３−３６％）が挙げられる。本発明には、酸化ポリエチレンの樹脂エマルジョンをそのまま本発明の農薬含有微粒子の製造に使用することができる。また、酸化ポリエチレンの樹脂エマルジョンは、市販の酸化ポリエチレンを水に分散させることによっても製造することができる。具体的には例えば、以下の方法により製造することができる。酸化ポリエチレンを加熱溶融し、必要に応じて界面活性剤（カチオン性界面活性剤、ノニオン性界面活性剤）を加え、これを攪拌下に９５〜９８℃の熱水中に加え、ポリカルボン酸の乳化液を調製する。この際、酸化ポリエチレンの融点に応じて、オートクレーブ容器等の加圧条件下で行う。酸化ポリエチレンが溶融した状態のままで、攪拌等により酸化ポリエチレンの粒径を整え、徐々に冷却して、酸化ポリエチレンの樹脂エマルジョンを得る。
本発明には、平均粒子径が通常１μｍ以下の酸化ポリエチレンが用いられる。
The polyethylene oxide used in the present invention can be produced, for example, as a resin emulsion in which polyethylene oxide is dispersed by oxygen-oxidizing a resin emulsion in which polyethylene is dispersed in water, or a resin emulsion in which polyethylene oxide is dispersed. Agrocer DCX 1688 (manufactured by Clariant, solid content: about 18%), and Polygen WE6 (manufactured by BOYSAN, solid content: 33-36%) can be mentioned. In the present invention, the resin emulsion of polyethylene oxide can be used as it is for the production of the agrochemical-containing fine particles of the present invention. The resin emulsion of oxidized polyethylene can also be produced by dispersing commercially available oxidized polyethylene in water. Specifically, for example, it can be produced by the following method. The polyethylene oxide is heated and melted, and if necessary, a surfactant (cationic surfactant, nonionic surfactant) is added, and this is added to hot water at 95 to 98 ° C. with stirring. Prepare an emulsion. Under the present circumstances, it carries out under pressurization conditions, such as an autoclave container, according to the melting point of polyethylene oxide. While the oxidized polyethylene is in a molten state, the particle diameter of the oxidized polyethylene is adjusted by stirring or the like, and then gradually cooled to obtain a resin emulsion of oxidized polyethylene.
In the present invention, polyethylene oxide having an average particle size of usually 1 μm or less is used.
本発明において、水難溶性農薬活性成分と酸化ポリエチレンとの重量比は、通常１：９９〜９５：５の範囲であり、好ましくは１０：９０〜８０：２０の範囲である。 In the present invention, the weight ratio of the poorly water-soluble pesticide active ingredient and polyethylene oxide is usually in the range of 1:99 to 95: 5, preferably in the range of 10:90 to 80:20.
本発明の農薬含有微粒子の製造方法は、水難溶性農薬活性成分と酸化ポリエチレンとを水に分散させた分散液を調製する工程と、該分散液を噴霧乾燥する工程を含む。
水難溶性農薬活性成分と酸化ポリエチレンとを水に分散させた分散液は、例えば、上記の酸化ポリエチレンを水に分散させた樹脂エマルジョンに、微粉砕（平均粒子径１〜７μｍ程度）した水難溶性農薬活性成分を加え、攪拌することにより調製される。
水難溶性農薬活性成分等を微粉砕する方法としては、例えばハンマーミルやジェットミル等の乾式粉砕法やビーズミル等の湿式粉砕法が挙げられる。
The method for producing agrochemical-containing fine particles of the present invention includes a step of preparing a dispersion in which a poorly water-soluble pesticide active ingredient and polyethylene oxide are dispersed in water, and a step of spray-drying the dispersion.
For example, a dispersion in which a water-insoluble pesticide active ingredient and polyethylene oxide are dispersed in water is, for example, a water-insoluble pesticide obtained by finely pulverizing (average particle size of about 1 to 7 μm) in a resin emulsion in which the above polyethylene oxide is dispersed in water. Prepared by adding active ingredient and stirring.
Examples of the method for finely pulverizing the poorly water-soluble agrochemical active ingredient include a dry pulverization method such as a hammer mill and a jet mill and a wet pulverization method such as a bead mill.
この分散液には、本発明の目的を達する範囲内で、界面活性剤、粉砕助剤、増粘剤等が含有されていてもよい。
界面活性剤としては例えば、非イオン性界面活性剤、カチオン性界面活性剤、両イオン性界面活性剤あるいはこれらの混合物が挙げられる。非イオン性界面活性剤として具体的には、例えばポリオキシエチレンカルボン酸エステル、ポリオキシエチレンポリオキシプロピレンアルキルアリールエーテル、ポリオキシエチレンポリオキシプロピレンブロック共重合体、ポリオキシエチレンアルキルアリールエーテル、ポリオキシエチレンアルキルエーテル、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、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレントリスチリルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、脂肪酸エステル、多価アルコール脂肪酸エステル、及びポリオキシエチレン多価アルコール脂肪酸エステルが挙げられる。その使用量は、水難溶性農薬活性成分と酸化ポリエチレンとの合計量１００重量部に対して、通常０．５〜３０重量部である。
The dispersion may contain a surfactant, a grinding aid, a thickener, and the like within the scope of achieving the object of the present invention.
Examples of the surfactant include nonionic surfactants, cationic surfactants, amphoteric surfactants, and mixtures thereof. Specific examples of the nonionic surfactant include polyoxyethylene carboxylic acid ester, polyoxyethylene polyoxypropylene alkyl aryl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene alkyl aryl ether, polyoxyethylene Ethylene alkyl ether, polyoxyethylene polyoxypropylene tristyryl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene tristyryl phenyl ether, polyoxyethylene fatty acid ester, fatty acid ester, polyhydric alcohol fatty acid ester, and polyoxyethylene poly And monohydric alcohol fatty acid esters. The usage-amount is 0.5-30 weight part normally with respect to 100 weight part of total amounts of a poorly water-soluble agrochemical active ingredient and oxidized polyethylene.
粉砕助剤としては、例えば非晶性二酸化珪素、珪藻土、カオリンクレー、ロウ石クレー、セリサイト、ジークライト、タルク、酸性白土、炭酸カルシウム及びベントナイトが挙げられる。その使用量は、水難溶性農薬活性成分と酸化ポリエチレンとの合計量１００重量部に対して、通常０．５〜５０重量部である。 Examples of the grinding aid include amorphous silicon dioxide, diatomaceous earth, kaolin clay, waxy clay, sericite, gequelite, talc, acid clay, calcium carbonate and bentonite. The usage-amount is 0.5-50 weight part normally with respect to 100 weight part of total amounts of a poorly water-soluble agrochemical active ingredient and oxidized polyethylene.
増粘剤としては、ポリビニルアルコールやカルボキシメチルセルロース、デキストリン、キサンタンガム、グアーガム、アラビアガム、アルギン酸、カゼイン、ゼラチン、ポリビニルピロリドン、カルボキシビニルポリマー、アクリル系ポリマー、デンプン誘導体、ヘテロ多糖類等の高分子系増粘剤及びベントナイト、ホワイトカーボン等の無機系増粘剤が挙げられる。その使用量は、水難溶性農薬活性成分と酸化ポリエチレンとの合計量１００重量部に対して、通常１〜１０重量部である。 Thickeners include polyvinyl alcohol, carboxymethylcellulose, dextrin, xanthan gum, guar gum, gum arabic, alginic acid, casein, gelatin, polyvinylpyrrolidone, carboxyvinyl polymer, acrylic polymer, starch derivative, heteropolysaccharide Examples thereof include inorganic thickeners such as a thickener and bentonite and white carbon. The usage-amount is 1-10 weight part normally with respect to 100 weight part of total amounts of a poorly water-soluble agrochemical active ingredient and oxidized polyethylene.
本発明の農薬含有微粒子は、前記の農薬活性成分と酸化ポリエチレンとが水に分散された分散液を噴霧乾燥することにより製造される。本発明において、噴霧乾燥とは、分散液中の分散媒である水を噴霧と同時に蒸発させて固体を析出させる技術を意味する。
本発明において前記の水難溶性農薬活性成分と酸化ポリエチレンとが水に分散された分散液の噴霧乾燥は、通常８０〜２００℃程度に加熱した乾燥空気の流れ中に前記の水難溶性農薬活性成分と酸化ポリエチレンとが水に分散された分散液を噴霧装置を用いて噴霧することにより行われる。噴霧された水難溶性農薬活性成分と酸化ポリエチレンとが水に分散された分散液は、乾燥空気の流れ中で水が蒸発して、本発明の農薬含有微粒子を形成する。
この場合に用いられる噴霧装置としては、例えばロータリー式、加圧ノズル式、及び二流体ノズル式が挙げられるが、二流体ノズル式が好ましい。
The agrochemical-containing fine particles of the present invention are produced by spray-drying a dispersion in which the agrochemical active ingredient and polyethylene oxide are dispersed in water. In the present invention, spray drying means a technique for precipitating a solid by evaporating water, which is a dispersion medium in a dispersion, simultaneously with spraying.
In the present invention, the spray-drying of the dispersion in which the poorly water-soluble pesticidal active ingredient and polyethylene oxide are dispersed in water is usually performed with the poorly water-soluble pesticidal active ingredient in the flow of dry air heated to about 80 to 200 ° C. It is carried out by spraying a dispersion liquid in which polyethylene oxide is dispersed in water using a spray device. In the dispersion liquid in which the sprayed poorly water-soluble pesticide active ingredient and polyethylene oxide are dispersed in water, water evaporates in the flow of dry air to form the pesticide-containing fine particles of the present invention.
Examples of the spray device used in this case include a rotary type, a pressurized nozzle type, and a two-fluid nozzle type, and a two-fluid nozzle type is preferable.
本発明の農薬含有微粒子の大きさ（粒子径）は、通常５〜３０μｍの範囲内である。この粒子径は、農薬活性成分と酸化ポリエチレンとが水に分散された分散液を噴霧乾燥する際の噴霧条件を変化させることで制御する。即ち、供給する噴霧液の噴霧圧を高くするか、噴霧液の供給量を少なくすることにより、小さな粒子径の農薬含有微粒子を製造することができる。更に、噴霧液中の固形分の濃度を小さくするか、噴霧液の粘度を低くすることにより、小さな粒子径の農薬含有微粒子を製造することができる。
農薬含有微粒子の粒子径は、レーザー回折法により測定することができる。例えば、レーザー回折式粒度分布測定装置(Laser diffraction particle size analyzer)ＳＡＬＤ−１１００（島津製作所製）が使用できる。
The size (particle diameter) of the agrochemical-containing fine particles of the present invention is usually in the range of 5 to 30 μm. This particle size is controlled by changing the spray conditions when spray-drying the dispersion in which the agrochemical active ingredient and polyethylene oxide are dispersed in water. That is, agrochemical-containing fine particles having a small particle diameter can be produced by increasing the spray pressure of the spray solution to be supplied or decreasing the supply amount of the spray solution. Furthermore, by reducing the concentration of the solid content in the spray liquid or decreasing the viscosity of the spray liquid, it is possible to produce agrochemical-containing fine particles having a small particle diameter.
The particle size of the pesticide-containing fine particles can be measured by a laser diffraction method. For example, a laser diffraction particle size analyzer SALD-1100 (manufactured by Shimadzu Corporation) can be used.
噴霧乾燥条件は、噴霧乾燥に使用する装置に応じて適宜設定することができる。例えば東京理化器械株式会社製スプレードライヤーＳＤ-１型を用いて二流体ノズルを用いる場合には試料送液流量５０〜５００ｍｌ／時間、噴霧空気圧０．２〜２．０ｋｇ／ｃｍ2、乾燥空気流量０．４〜１．０ｍ3／分、乾燥空気入口温度１００〜２００℃、乾燥空気出口温度５０〜１００℃である。 The spray drying conditions can be appropriately set according to the apparatus used for spray drying. For example, when a two-fluid nozzle is used using a spray dryer SD-1 type manufactured by Tokyo Rika Kikai Co., Ltd., the sample feed flow rate is 50 to 500 ml / hour, the spray air pressure is 0.2 to 2.0 kg / cm 2 , and the dry air flow rate. 0.4 to 1.0 m 3 / min, dry air inlet temperature 100 to 200 ° C., and dry air outlet temperature 50 to 100 ° C.
前述の製造方法で本発明の農薬含有微粒子を製造すると、本発明の農薬含有微粒子が多数固着して団粒化する場合がある。この場合には、得られた粒子を粉砕機等により解砕することで、本発明の農薬含有微粒子を得ることができる。 When the agrochemical-containing fine particles of the present invention are produced by the above-described production method, a large number of the agrochemical-containing fine particles of the present invention may be fixed and aggregated. In this case, the agrochemical-containing fine particles of the present invention can be obtained by crushing the obtained particles with a pulverizer or the like.
本発明の農薬含有微粒子は、例えばそのまま水に懸濁させて、農薬活性成分の有効量を土壌や植物に施用することで使用することができる。
また、本発明の農薬含有微粒子は、固体担体、液体担体等の不活性担体とを混合し、必要に応じて界面活性剤、その他の製剤用補助剤を添加して、水和剤、顆粒水和剤、フロアブル剤等に製剤化されることも可能である。本発明の農薬徐放性粒子がさらに製剤化された場合には、その製剤形態に応じて、通常の農薬施用方法により使用することができる。
The agrochemical-containing fine particles of the present invention can be used, for example, by suspending them in water as they are and applying an effective amount of the agrochemical active ingredient to soil or plants.
The agrochemical-containing fine particles of the present invention are mixed with an inert carrier such as a solid carrier and a liquid carrier, and if necessary, a surfactant and other adjuvants for preparation are added to obtain a wettable powder, granular water. It is also possible to formulate into a balm or flowable. When the agrochemical sustained-release particles of the present invention are further formulated, they can be used according to a conventional agrochemical application method depending on the formulation form.
本発明の農薬含有微粒子は、農薬活性成分が徐放化されたものであり、また水に懸濁させた場合に分散状態の持続性に優れるものである。 The agrochemical-containing fine particles of the present invention are those in which an agrochemical active ingredient is sustained-released and are excellent in sustainability in a dispersed state when suspended in water.
次に製造例、試験例等により本発明をさらに詳細に説明するが、本発明はこれらの例に限定されるものではない。 Next, the present invention will be described in more detail with reference to production examples and test examples, but the present invention is not limited to these examples.
製造例１
酸化ポリエチレン樹脂エマルジョン（Agrocer 06；酸化ポリエチレン（融点：１１５℃、平均粒子径：０．１９μｍ、酸価：１６〜１９ｍｇＫＯＨ／ｇ）の２５重量％懸濁液；クラリアント社製）４０重量部と水４０重量部との混合物に、フルミオキサジン（平均粒子径：３．３μｍ、ジェットミルにより粉砕）２０重量部を加えて攪拌し、分散液を調製した。この分散液を下記の条件で噴霧乾燥し、得られた固形物を粉砕機（スクリーン径：１．５ｍｍ、回転数１００００ｒｐｍ、日本精機製作所製）で解砕して、本発明の農薬含有微粒子（平均粒子径：１１．１μｍ）を得た。
Production Example 1
40 parts by weight of oxidized polyethylene resin emulsion (Agrocer 06; 25% by weight suspension of oxidized polyethylene (melting point: 115 ° C., average particle size: 0.19 μm, acid value: 16-19 mg KOH / g); manufactured by Clariant) To the mixture with 40 parts by weight, 20 parts by weight of flumioxazin (average particle size: 3.3 μm, ground by a jet mill) was added and stirred to prepare a dispersion. The dispersion was spray-dried under the following conditions, and the obtained solid was pulverized with a pulverizer (screen diameter: 1.5 mm, rotation speed: 10000 rpm, manufactured by Nippon Seiki Seisakusho). An average particle size: 11.1 μm) was obtained.
噴霧乾燥の条件
噴霧乾燥機：東京理化器械株式会社製 ＳＤ−１型噴霧乾燥機
噴霧装置：試料噴出ノズル直径０．５１ｍｍの二流体ノズル
試料送液流量：２００ｍｌ／時間
試料噴霧空気圧：０．７ｋｇ／ｃｍ2
乾燥空気流量：０．６ｍ3／分
乾燥空気入口温度：１１５℃
乾燥空気出口温度：６５℃
Spray drying conditions Spray dryer: SD-1 type spray dryer manufactured by Tokyo Rika Kikai Co., Ltd. Spray device: Two-fluid nozzle with a sample ejection nozzle diameter of 0.51 mm Sample feed flow rate: 200 ml / hour Sample spray air pressure: 0.7 kg / Cm 2
Dry air flow rate: 0.6 m 3 / min Dry air inlet temperature: 115 ° C
Dry air outlet temperature: 65 ° C
製造例２
酸化ポリエチレン樹脂エマルジョン（Agrocer 06；酸化ポリエチレン（融点：１１５℃、平均粒子径：０．１９μｍ、酸価：１６〜１９ｍｇＫＯＨ／ｇ）の２５重量％懸濁液；クラリアント社製）４０重量部、水５０重量部、及びフルミオキサジン（平均粒子径：３．３μｍ）１０重量部を使用し、製造例１と同様にして本発明の農薬含有微粒子（平均粒子径９．１μｍ）を得た。
Production Example 2
40 parts by weight of an oxidized polyethylene resin emulsion (Agrocer 06; 25% by weight suspension of oxidized polyethylene (melting point: 115 ° C., average particle size: 0.19 μm, acid value: 16-19 mg KOH / g); manufactured by Clariant) 50 parts by weight and 10 parts by weight of flumioxazin (average particle size: 3.3 μm) were used in the same manner as in Production Example 1 to obtain agrochemical-containing fine particles (average particle size of 9.1 μm) of the present invention.
製造例３
酸化ポリエチレン樹脂エマルジョン（Agrocer 06；酸化ポリエチレン（融点：１１５℃、平均粒子径：０．１９μｍ、酸価：１６〜１９ｍｇＫＯＨ／ｇ）の２５重量％懸濁液；クラリアント社製）６０重量部、水２５重量部、及びフルミオキサジン（平均粒子径：３．３μｍ）１５重量部を使用し、製造例１と同様にして本発明の農薬含有微粒子を得る。
Production Example 3
60 parts by weight of oxidized polyethylene resin emulsion (Agrocer 06; 25% by weight suspension of oxidized polyethylene (melting point: 115 ° C., average particle size: 0.19 μm, acid value: 16 to 19 mg KOH / g); manufactured by Clariant) 25 parts by weight and 15 parts by weight of flumioxazin (average particle size: 3.3 μm) are used in the same manner as in Production Example 1 to obtain the agrochemical-containing fine particles of the present invention.
製造例４
酸化ポリエチレン樹脂エマルジョン（Agrocer 06；酸化ポリエチレン（融点：１１５℃、平均粒子径：０．１９μｍ、酸価：１６〜１９ｍｇＫＯＨ／ｇ）の２５重量％懸濁液；クラリアント社製）８０重量部、及びフルミオキサジン（平均粒子径：３．３μｍ）２０重量部を用い、製造例１と同様にして本発明の農薬含有微粒子（平均粒子径１５．９μｍ）を得た。
Production Example 4
80 parts by weight of oxidized polyethylene resin emulsion (Agrocer 06; 25% by weight suspension of oxidized polyethylene (melting point: 115 ° C., average particle size: 0.19 μm, acid value: 16-19 mg KOH / g); manufactured by Clariant) Using 20 parts by weight of flumioxazin (average particle size: 3.3 μm), the agrochemical-containing fine particles (average particle size of 15.9 μm) of the present invention were obtained in the same manner as in Production Example 1.
製造例５
酸化ポリエチレン樹脂エマルジョン（Agrocer 06；酸化ポリエチレン（融点：１１５℃、平均粒子径：０．１９μｍ、酸価：１６〜１９ｍｇＫＯＨ／ｇ）の２５重量％懸濁液；クラリアント社製）８０重量部、水１０重量部、及びフルミオキサジン（平均粒子径：３．３μｍ）１０重量部を用い、製造例１と同様にして本発明の農薬含有微粒子（平均粒子径１１．９μｍ）を得た。
Production Example 5
80 parts by weight of oxidized polyethylene resin emulsion (Agrocer 06; 25% by weight suspension of oxidized polyethylene (melting point: 115 ° C., average particle size: 0.19 μm, acid value: 16 to 19 mg KOH / g); manufactured by Clariant) 10 parts by weight and 10 parts by weight of flumioxazin (average particle size: 3.3 μm) were used in the same manner as in Production Example 1 to obtain the agrochemical-containing fine particles (average particle size 11.9 μm) of the present invention.
比較製造例１
ポリエチレン樹脂エマルジョン（Hordamer PE03；ポリエチレン（融点：９６℃、平均粒子径：０．１７μｍ）の４０重量％懸濁液；クラリアント社製）２５重量部と水５５重量部との混合物にフルミオキサジン（平均粒子径：３．３μｍ、ジェットミルにより粉砕）２０重量部を加えて攪拌し、分散液を調製した。この分散液を、製造例１と同じ条件で噴霧乾燥、解砕して、農薬含有粒子を得た。
Comparative production example 1
Flumioxazin (average) in a mixture of 25 parts by weight of polyethylene resin emulsion (Hordamer PE03; polyethylene (melting point: 96 ° C., average particle size: 0.17 μm), 40% by weight suspension; Clariant) and water (Particle size: 3.3 μm, pulverized with a jet mill) 20 parts by weight were added and stirred to prepare a dispersion. This dispersion was spray-dried and crushed under the same conditions as in Production Example 1 to obtain agrochemical-containing particles.
比較製造例２
ポリエチレン樹脂エマルジョン（Hordamer PE03；ポリエチレン（融点：９６℃、平均粒子径：０．１７μｍ）の４０重量％懸濁液；クラリアント社製）５０重量部と水３０重量部との混合物にフルミオキサジン（平均粒子径：３．３μｍ、ジェットミルにより粉砕）２０重量部を加えて攪拌し、分散液を調製した。この分散液を、製造例１と同じ条件で噴霧乾燥、解砕して、農薬含有粒子を得た。
Comparative production example 2
Flumioxazin (average) in a mixture of 50 parts by weight of a polyethylene resin emulsion (Hordamer PE03; polyethylene (melting point: 96 ° C., average particle size: 0.17 μm), 40% by weight; Clariant) and 30 parts by weight of water (Particle size: 3.3 μm, pulverized with a jet mill) 20 parts by weight were added and stirred to prepare a dispersion. This dispersion was spray-dried and crushed under the same conditions as in Production Example 1 to obtain agrochemical-containing particles.
試験例１
３４２ｐｐｍ硬水（ＣＩＰＡＣ標準水）５０ｍｌに、均一に分散された場合にフルミオキサジン換算で５００ｐｐｍの濃度となる量の農薬含有微粒子を加え懸濁させた。
一方、２５０ｍｌ有栓メスシリンダーに３４２ｐｐｍ硬水（ＣＩＰＡＣ標準水）２００ｍｌを入れて、３０℃に保った。ここに、前記の農薬含有微粒子の懸濁液を加え、栓をして、１分間に３０回転倒させた。
その後、３０℃で３０分間静置してから、メスシリンダーの目盛りが１２５ｍｌの付近の懸濁液２５ｍｌを採取した。この採取した懸濁液に含有されるフルミオキサジンの量を高速液体クロマトグラフィーにより定量分析し、下式により懸垂率を求めた。
Test example 1
In 50 ml of 342 ppm hard water (CIPAC standard water), agrochemical-containing fine particles were added and suspended in an amount to give a concentration of 500 ppm in terms of flumioxazin when uniformly dispersed.
On the other hand, 200 ml of 342 ppm hard water (CIPAC standard water) was placed in a 250 ml stoppered graduated cylinder and kept at 30 ° C. The above-mentioned suspension of the agrochemical-containing fine particles was added thereto, stoppered, and tilted 30 times per minute.
Then, after leaving still at 30 degreeC for 30 minute (s), 25 ml of suspensions whose scale of the graduated cylinder was 125 ml were extract | collected. The amount of flumioxazin contained in the collected suspension was quantitatively analyzed by high performance liquid chromatography, and the suspension rate was determined by the following equation.
懸垂率（％）＝｛（採取した懸濁液中のフルミオキサジン量）／（試験に用いた農薬含有微粒子中に含有されるフルミオキサジン全量／１０）｝×１００
結果を表１に示す。
Suspension rate (%) = {(flumioxazine amount in the collected suspension) / (total amount of flumioxazin contained in the agricultural chemical-containing fine particles used in the test / 10)} × 100
The results are shown in Table 1.
次に、本発明の農薬含有微粒子が徐放性能を有することを、水への高倍率希釈条件における溶出試験にて示す。
試験例２
上述の製造例１及び製造例４により得た本発明の農薬含有微粒子の所定量とイオン交換水１Ｌとを混合し、水温２５℃で緩やかに６時間攪拌した。その後に、ビーカー中央部から試験液１００ｍｌを採取して、濾過し、得られた固形分からフルミオキサジンを抽出し、固形分に含有されるフルミオキサジン量を高速液体クロマトグラフィーにより定量した。この結果から、６時間後の本発明の農薬含有微粒子からのフルミオキサジンの溶出率を求めた。
結果を表２に示す。高倍率希釈条件においても本発明の農薬含有微粒子に農薬活性成分が保持されており、徐放性を有することが判る。
Next, it is shown by a dissolution test under high-dilution dilution conditions in water that the agricultural chemical-containing fine particles of the present invention have sustained release performance.
Test example 2
A predetermined amount of the agrochemical-containing fine particles of the present invention obtained in Production Example 1 and Production Example 4 described above and 1 L of ion-exchanged water were mixed and gently stirred at a water temperature of 25 ° C. for 6 hours. Thereafter, 100 ml of the test solution was collected from the center of the beaker and filtered, and flumioxazin was extracted from the obtained solid, and the amount of flumioxazin contained in the solid was quantified by high performance liquid chromatography. From this result, the elution rate of flumioxazin from the agricultural chemical-containing fine particles of the present invention after 6 hours was determined.
The results are shown in Table 2. It can be seen that the pesticidal active ingredient is retained in the pesticidal-containing microparticles of the present invention even under high-magnification dilution conditions, and has sustained release properties.
本発明の農薬含有微粒子は、優れた特性を有するので、それ自体農薬製剤として有用であり、また農薬製剤の原料としても好適である。 Since the agrochemical-containing fine particles of the present invention have excellent characteristics, they are useful as agrochemical formulations themselves and are also suitable as raw materials for agrochemical formulations.
Claims (5)
A method for producing agrochemical-containing fine particles, comprising: preparing a dispersion in which a water-insoluble pesticide active ingredient and polyethylene oxide are dispersed in water; and spray-drying the dispersion.
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| JP2004326019A Expired - Fee Related JP4655592B2 (en) | 2003-11-12 | 2004-11-10 | Pesticide-containing fine particles and method for producing the same |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62277301A (en) * | 1986-01-31 | 1987-12-02 | Takeda Chem Ind Ltd | Sustained release agricultural chemical composition |
| JPH04370177A (en) * | 1991-06-19 | 1992-12-22 | Fukuvi Chem Ind Co Ltd | Floor wax |
| JPH10265301A (en) * | 1997-03-03 | 1998-10-06 | Rohm & Haas Co | Agrochemical composition |
| JP2000239105A (en) * | 1999-02-16 | 2000-09-05 | Agrevo Japan Kk | Control-release agrochemical formulation and its production |
| JP2001055303A (en) * | 1999-08-12 | 2001-02-27 | Toho Chem Ind Co Ltd | Agrochemical granule having controlled release function |
-
2004
- 2004-11-10 JP JP2004326019A patent/JP4655592B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62277301A (en) * | 1986-01-31 | 1987-12-02 | Takeda Chem Ind Ltd | Sustained release agricultural chemical composition |
| JPH04370177A (en) * | 1991-06-19 | 1992-12-22 | Fukuvi Chem Ind Co Ltd | Floor wax |
| JPH10265301A (en) * | 1997-03-03 | 1998-10-06 | Rohm & Haas Co | Agrochemical composition |
| JP2000239105A (en) * | 1999-02-16 | 2000-09-05 | Agrevo Japan Kk | Control-release agrochemical formulation and its production |
| JP2001055303A (en) * | 1999-08-12 | 2001-02-27 | Toho Chem Ind Co Ltd | Agrochemical granule having controlled release function |
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| JP4655592B2 (en) | 2011-03-23 |
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