JP7110117B2 - エマルションポリマーに基づく農薬製剤 - Google Patents
エマルションポリマーに基づく農薬製剤 Download PDFInfo
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- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
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- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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Description
(a) 室温で固体である少なくとも1種類の農薬活性化合物の水性分散液;
(b) (I)安定剤ポリマー(stabiliser polymer);及び、(II)コア-安定剤コポリマー(core-stabiliser copolymer)を含んでいるエマルションポリマー系〔ここで、該(I)安定剤ポリマーは、酸と疎水性物質の重量/数比(weight/number ratio)が10-90:90-10である酸に基づく疎水性モノマーを含んでおり、30℃~300℃の範囲内のTgを有しており、及び、100,000未満の分子量を有しており;及び、該(II)コアポリマーは、-100℃~10℃の範囲内のTgを有している〕;及び、
(c) 非イオン性又はアニオン性の界面活性剤又は分散助剤からなる群から選択される1種類以上の添加剤;
(d) レオロジー改質剤;及び、
(e) 別の製剤助剤;
を含んでいる農薬組成物を対象とする。
(f) 浸透促進剤、湿潤剤、展着剤(spreading agent)、及び/又は、保持剤(retention agent);
も含んでいることができる。
・ イミダクロプリド、ニテンピラム、アセタミプリド、チアクロプリド、チアメトキサム、クロチアニジン;
・ シアントラニルプロール、クロラントラニリプロール、フルベンジアミド、テトラニリプロール、シクラニリプロール;
・ スピロジクロフェン、スピロメシフェン、スピロテトラマト;
・ アバメクチン、アクリナトリン、クロルフェナピル、エマメクチン、エチプロール、フィプロニル、フロニカミド、フルピラジフロン、インドキサカルブ、メタフルミゾン、メトキシフェノジド、ミルベマイシン、ピリダベン、ピリダリル、シラフルオフェン、スピノサド、スルホキサフロル、トリフルムロン;
・ WO 2006/089633の中で実施例I-1-a-4として記載されている化合物、WO 2008/067911の中で実施例I-1-a-4として記載されている化合物、WO 2013/092350の中で実施例Ib-14として記載されている化合物、WO 2010/51926の中で実施例Ik-84として記載されている化合物。
該ビニル芳香族モノマーがスチレンと置換されているスチレンの混合物である場合、そのモノマー混合物は、80-95重量%の範囲内のスチレン及び5-20重量%の範囲内の置換されているスチレンを含有し得る。
・ コアポリマーは、75%アクリル酸2-エチルヘキシル 25%スチレンであり、安定剤ポリマーは、65%アクリル酸 35%スチレンであり、ナトリウム塩(100%)、分子量 約10,000Da、コア:安定剤比 70:30、測定された固形物の割合(%) 46%。
・ キサンタンガム、グアーガム及びヒドロキシエチルセルロースを包含する多糖類: その例は、Kelzan(登録商標)、Rhodopol(登録商標) G、Rhodopol(登録商標) 23、Satiaxane(登録商標) CX911、及び、Natrosol(登録商標) 250 rangeである;
・ モンモリロナイト、ベントナイト、セピオライト(sepeolite)、アタパルジャイト、ラポナイト、ヘクトライトを包含するクレー: その例は、Veegum(登録商標) R、Van Gel(登録商標) B、Bentone(登録商標) CT、Bentone(登録商標) HC、Bentone(登録商標) EW、Pangel(登録商標) M100、Pangel(登録商標) M200、Pangel(登録商標) M300、Pangel(登録商標) S、Pangel(登録商標) M、Pangel(登録商標) W、Attagel(登録商標) 50、Laponite(登録商標) RDである;
・ ヒュームドシリカ及び沈降シリカ: その例は、Aerosil(登録商標) 200、Siponat(登録商標) 22である。
使用可能な防腐剤は、この目的のために農薬において慣習的に使用可能な全ての物質である。防腐剤に関する適切な例は、5-クロロ-2-メチル-4-イソチアゾリン-3-オン[CAS-No.26172-55-4]、2-メチル-4-イソチアゾリン-3-オン[CAS-No.2682-20-4]又は1.2-ベンゾイソチアゾール-3(2H)-オン[CAS-No.2634-33-5]を含んでいる調製物である。挙げることができる例は、Preventol(登録商標) D7(Lanxess)、Kathon(登録商標) CG/ICP(Dow)、Acticide(登録商標) SPX(Thor GmbH)、及び、Proxel(登録商標) GXL(Arch Chemicals)である。
・ 2-20のEO単位を有するエトキシ化分枝鎖アルコール(例えば、Genapol(登録商標) X-型);
・ 2-20のEO単位を含んでいるメチル末端キャップエトキシ化分枝鎖アルコール(例えば、Genapol(登録商標) XM-型);
・ 2-20のEO単位を含んでいるエトキシ化ヤシアルコール(例えば、Genapol(登録商標) C-型);
・ 2-20のEO単位を含んでいるエトキシ化C12/15アルコール(例えば、Synperonic(登録商標) A-型);
・ 直鎖又は分枝鎖のプロポキシ-エトキシ化アルコール、例えば、Antarox(登録商標) B/848、Atlas(登録商標) G5000、Lucramul(登録商標) HOT 5902;
・ Me末端キャッププロポキシ-エトキシ化脂肪酸、例えば、Leofat(登録商標) OC0503M;
・ 有機変性ポリシロキサン、例えば、BreakThru(登録商標) OE444、BreakThru(登録商標) S240、Silwett(登録商標) L77、Silwett(登録商標) 408、Silwet(登録商標) 806;
・ 1-10個の炭素原子を含んでいる分枝鎖アルコール又は直鎖アルコールを有するスルホコハク酸Na塩のモノエステル及びジエステル;
・ エトキシ化ジアセチレン-ジオール(例えば、Surfynol(登録商標) 4xx-range);
・ アルキルエーテルシトレート界面活性剤(例えば、Adsee CE range、Akzo Nobel);
・ アルキルポリサッカリド(例えば、Agnique(登録商標) PG8107、Agnique(登録商標) PG8105、Atplus(登録商標) 438、Atplus(登録商標) AL-2559、Atplus(登録商標) AL-2575);
・ 8-18個の炭素原子及び平均して10-40のEO単位を有する脂肪酸を含んでいるグリセリンのエトキシ化モノエステル又はエトキシ化ジエステル(例えば、Crovol(登録商標) range);
・ 平均して5-40のEO単位を含んでいるヒマシ油エトキシレート(例えば、Berol(登録商標) range、Emulsogen(登録商標) EL range);
・ ポリエチレンオキシドとポリプロピレンオキシドのブロックコポリマー。
・ ヒマワリ油、ナタネ油、トウモロコシ油、ダイズ油、米ぬか油、オリーブ油;
・ オレイン酸エチルヘキシル、パルミチン酸エチルヘキシル、ミリスチン酸/ラウリン酸エチルヘキシル、ラウリン酸エチルヘキシル、カプリル酸/カプリン酸エチルヘキシル、ミリスチン酸イソ-プロピル、パルミチン酸イソ-プロピル、オレイン酸メチル、パルミチン酸メチル、オレイン酸エチル、ナタネ油メチルエステル、ダイズ油メチルエステル、米ぬか油メチルエステル;
・ Exxsol(登録商標) D100、Solvesso(登録商標) 200ND。
実施例
(A)方法
耐雨性は、以下の方法に従って確認した。
リンゴのクチクラのディスクを中粘度シリコーン油の薄層を用いてリンゴの外表面が上向きになるようにガラス顕微鏡スライドに固定した。これに、5% CIPAC C水を含んでいる脱イオン水で0.5%~1%に希釈された種々の製剤の1μLの液滴をマイクロピペットを用いて施用し、1時間放置して乾燥させた。各付着量について、交差偏光フィルターが付いている光学透過型顕微鏡で調査し、画像を記録した。該製剤の乾燥した液滴が付いているクチクラを含んでいるスライドを、穏やかに流れる脱イオン水(タップ放水口の下方10cmの高さで、流量約300mL/分)の下に15秒間保持した。そのガラススライドを乾燥させ、該付着量を前記顕微鏡で再度調査し、最初の画像と比較した。洗い流された活性成分の量を視覚的に評価し、以下の量で記録した:>90%、75%、50%、25%、及び、<10%。2反復で測定し、2反復の平均値を記録した。
懸濁製剤の調製方法は、当技術分野において知られており、そして、当業者がよく知っている既知方法で製造することができる。水中のキサンタンの2%ゲル及び殺生物剤(e)を低剪断撹拌で調製した。活性成分(a)、非イオン性分散剤及びアニオン性分散剤(c)及び別の製剤助剤(e)を混合させてスラリーを形成させ、最初に、高剪断ローター・ステーターミキサーで混合して粒径D(v,0.9)を約50ミクロンまで低減させ、次いで、1以上のビーズミルを通して、該活性成分の生物学的効能にとって必要とされる典型的には1~15ミクロンの粒径D(v,0.9)を達成した。当業者は、これが異なる活性成分にとってさまざまであり得るということを理解する。ポリマー分散液(b)及びキサンタンゲルを添加し、均質になるまで、低剪断撹拌で混合した。
サスポエマルション製剤の調製方法は、当技術分野において知られており、そして、当業者がよく知っている既知方法で製造することができる。水中のキサンタンの2%ゲル及び殺生物剤(e)を低剪断撹拌で調製した。活性成分スピロキサミン(a)、油(e)及び酸化防止剤(e)を混合させ、そして、非イオン性分散剤(c)の一部分(32g/L)を含んでいる水性分散液に、典型的には1~5ミクロンの液滴直径D(v,0.9)を有する水中油型エマルションが形成されるまで、ローター・ステーターミキサーを用いて高剪断混合しながら添加した。活性成分フルオピラム(a)、残りの非イオン性分散剤及びアニオン性分散剤(c)及び別の残りの製剤助剤(e)を残りの水と混合させてスラリーを形成させ、最初に、高剪断ローター・ステーターミキサーで混合して粒径D(v,0.9)を約50ミクロンまで低減させ、次いで、1以上のビーズミルを通して、該活性成分の生物学的効能にとって必要とされる典型的には1~15ミクロンの粒径D(v,0.9)を達成した。当業者は、これが異なる活性成分にとってさまざまであり得るということを理解する。水中油型エマルション、ポリマー分散液(b)及びキサンタンゲルを添加し、均質になるまで、低剪断撹拌で混合した。
1つのサンプルを45℃で1週間貯蔵し、及び、もう1つのサンプルについては、夜間、-30℃、及び、日中、室温(RT;22℃)で、又は、夜間、-15℃、及び、日中、30℃での貯蔵を、5~8サイクル実施して、実施例の製剤の安定性について確認した。次いで、それらを、増粘について視覚的に調査し、及び、水で1%に稀釈したものを、活性成分粒子の凝集の兆候について顕微鏡で調査した。実施例2の篩残(sieve retention)は、各実施例の製剤の1%懸濁液の50mLを150ミクロンの篩を通して注ぎ、水で濯ぎ洗い、そして、篩の残渣を視覚的に確認することによって求めた。
製剤は、以下の配合で調製した:
別の実施例において、配合3(本発明)及びNativo(登録商標) WGの生物学的効能について、屋外で、水稲で比較した。イネ葉いもち病及びイネ穂いもち病(neck rice blast disease)に対する生物学的効力について、2回目の茎葉噴霧施用の13-15日後(評価1)及び2回目又は3回目の茎葉噴霧施用の21-35日後(評価2)に評価し、並びに、収穫時に収穫量を測定した。
Claims (8)
- 農薬組成物であって、
(a) 室温で固体である少なくとも1種類の農薬活性化合物の水性分散液;
(b) (I)安定剤ポリマー;及び、(II)コア-安定剤コポリマーを含んでいるエマルションポリマー系〔ここで、該(I)安定剤ポリマーは、酸と疎水性物質の重量/数比が10-90:90-10である酸に基づく及び疎水性モノマーを含んでおり、30℃~300℃の範囲内のTgを有しており、及び、100,000未満の分子量を有しており;及び、該(II)コア-安定剤コポリマーは、-100℃~10℃の範囲内のTgを有している〕;及び、
(c) 非イオン性又はアニオン性の界面活性剤又は分散助剤からなる群から選択される1種類以上の添加剤;
(d) レオロジー改質剤;及び、
(e) 別の製剤助剤;
を含んでいる、前記農薬組成物。 - 前記別の製剤助剤として浸透促進剤、湿潤剤、展着剤及び/又は保持剤を含んでいることを特徴とする、請求項1に記載の農薬組成物。
- 茎葉散布のための、請求項1に記載の農薬組成物の使用。
- 農業害虫、雑草又は病害と闘うための、又は、農業害虫、雑草又は病害を防除するための、請求項1に記載の農薬組成物の使用。
- その中に含まれている農薬活性化合物を植物及び/又はそれらの生息環境に施用するための、請求項1に記載の農薬組成物の使用。
- 農薬活性成分の耐雨性を向上させるための、請求項1に記載の農薬組成物の使用。
- 降雨による洗脱に対する農薬活性成分の耐性を向上させるための、請求項1に記載の農薬組成物の使用。
- 環境中への農薬活性成分の的外れな損失を低減させるための、請求項1に記載の農薬組成物の使用。
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UA126797C2 (uk) | 2023-02-08 |
MX2018014494A (es) | 2019-04-15 |
CL2018003329A1 (es) | 2019-03-15 |
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UY37259A (es) | 2018-01-02 |
KR102505381B1 (ko) | 2023-03-02 |
AU2021266333A1 (en) | 2021-12-09 |
TW201808097A (zh) | 2018-03-16 |
CN109414012A (zh) | 2019-03-01 |
EP3248465A1 (en) | 2017-11-29 |
AU2017271468A1 (en) | 2018-12-06 |
BR112018074088A2 (pt) | 2019-03-06 |
RU2018145743A3 (ja) | 2020-07-09 |
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EP3462864A1 (en) | 2019-04-10 |
BR112018074088B1 (pt) | 2022-08-23 |
RU2018145743A (ru) | 2020-06-25 |
TWI767912B (zh) | 2022-06-21 |
RU2761641C2 (ru) | 2021-12-13 |
US20200315165A1 (en) | 2020-10-08 |
AR108572A1 (es) | 2018-09-05 |
CO2018012510A2 (es) | 2018-12-14 |
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