JP3963570B2 - Plant disease control composition - Google Patents

Description

［式中、Ｑは水素原子、メチル基、トリフルオロメチル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メトキシ基、メチルチオ基、メチルスルホキシ基、メチルスルホニル基、シアノ基、アセチル基、ニトロ基、アルコキシカルボニル基またはアミノ基を示し、Ｒは炭素数１〜１２の直鎖または分岐のアルキル基、炭素数１〜１２の直鎖または分岐のハロゲノアルキル基、炭素数２〜１０の直鎖または分岐のアルケニル基、炭素数２〜１０の直鎖または分岐のハロゲノアルケニル基、炭素数２〜１０のアルキルチオアルキル基、炭素数２〜１０のアルキルオキシアルキル基、炭素数１〜４のアルキル基で置換していてもよい炭素数３〜１０のシクロアルキル基、炭素数１〜４のアルキル基で置換していてもよい炭素数３〜１０のハロゲノ置換シクロアルキル基、または１〜３個の置換基により置換されていてもよいフェニル基であり、該フェニル基の置換基は水素原子、炭素数１〜４のアルキル基、炭素数２〜４のアルケニル基、炭素数２〜４のアルキニル基、炭素数３〜６のシクロアルキル基、炭素数１〜４のアルコキシ基、炭素数１〜４のハロゲノアルコキシ基、炭素数１〜４のアルキルチオ基、炭素数１〜４のアルキルスルホキシ基、炭素数１〜４のアルキルスルホニル基、ハロゲン原子、シアノ基、炭素数２〜４のアシル基、炭素数２〜４のアルコキシカルボニル基、アミノ基、または炭素数１〜３のアルキル基で置換されたアミノ基であり、Ｒと−ＮＨＣＯＡｒは互いに隣り合っており、Ａｒは以下の（Ａ１）から（Ａ８）（化４）
【０００９】
【化４】

（式中、Ｒ1 はトリフルオロメチル基、ジフルオロメチル基、メチル基、エチル基、塩素原子、臭素原子またはヨウ素原子であり、Ｒ2 は水素原子、メチル基、トリフルオロメチル基またはアミノ基であり、ｎは０〜２の整数である）で表される基である］で表される置換チオフェン誘導体であり、成分ＩＩはフルジオキソニル、アニリノピリミジン系化合物、フルアジナム、イミノクタジン アルベシル酸塩またはポリオキシンのうちの少なくとも一つを含有する組成物に関する。
【００１０】
本発明組成物を使用することにより、慣用の方法に比べて予期しない少量の有効成分量で、効果的に病害を防除できる。また、本剤は、灰色かび病に対する相乗効果のほか、うどんこ病、赤さび病等に対しても高い効果を示す点は、大きなメリットである。
【００１１】
【発明の実施の形態】
本発明の成分Ｉで表される化合物のうち、好ましいものは、Ａｒが（Ａ１）で、Ｒ1 がＣＦ₃ またはＭｅ基であり、Ｒ2 がＭｅ基；Ａｒが（Ａ２）で、Ｒ1 がＣＦ₃ またはＣＨＦ₂ 基；Ａｒが（Ａ３）で、Ｒ1 はＭｅ基であり、Ｒ2 は水素原子またはＭｅ基；Ａｒが（Ａ４）で、Ｒ1 はＭｅ基であり、ｎは０〜１；Ａｒが（Ａ５）であり、Ｒ1 は塩素原子；Ａｒが（Ａ６）または（Ａ７）；Ａｒが（Ａ８）で、Ｒ1 がＭｅ基であり、Ｒが炭素数４〜８の直鎖または分岐のアルキル基、または炭素数１〜４のアルキル基で置換していてもよい炭素数４〜８のシクロアルキル基で表される化合物である。特に好ましいものは、Ａｒが（Ａ１）で、Ｒ1 がＣＦ₃ またはＭｅ基であり、Ｒ2 がＭｅ基；Ａｒが（Ａ２）であり、Ｒ1 がＣＦ₃ またはＣＨＦ₂ 基であり、Ｒ3 が水素原子であり、Ｒが炭素数４〜８の直鎖または分岐のアルキル基、または炭素数１〜４のアルキル基で置換してもよい炭素数４〜８のシクロアルキル基で表される化合物である。
【００１２】
以下に、成分Ｉで表される化合物の具体例の幾つかを示す。
化合物番号１： Ｎ−｛２−（１，３−ジメチルブチル）−３−チエニル｝−２，４−ジメチルチアゾール−５−カルボン酸アミド
[Ｒが１，３−ジメチルブチル基であり、ＡｒがＡ１（Ｒ１＝Ｍｅ，Ｒ２＝Ｍｅ）の場合]
化合物番号２： Ｎ−｛２−（１，３−ジメチルブチル）−３−チエニル｝−３−トリフルオロメチル−１−メチルピラゾール−４−カルボン酸アミド
[Ｒが１，３−ジメチルブチル基であり、ＡｒがＡ２（Ｒ１＝ＣＦ₃）の場合]
化合物番号３： Ｎ−｛２−（１，３−ジメチルブチル）−３−チエニル｝−２−メチルフラン−３−カルボン酸アミド
[Ｒが１，３−ジメチルブチル基であり、ＡｒがＡ３（Ｒ１＝Ｍｅ，Ｒ２＝Ｈ）の場合]
化合物番号４： Ｎ−｛２−（１，３−ジメチルブチル）−３−チエニル｝−３−メチルチオフェン−２−カルボン酸アミド
[Ｒが１，３−ジメチルブチル基であり、ＡｒがＡ４（Ｒ１＝Ｍｅ，ｎ＝０）の場合]
化合物番号５： Ｎ−｛２−（１，３−ジメチルブチル）−３−チエニル｝−２−クロロニコチン酸アミド
[Ｒが１，３−ジメチルブチル基であり、ＡｒがＡ６の場合]
本発明の組成物は、下記の種類の植物病害に対して有効である：イネのいもち病(Pyricularia oryzae)、紋枯病(Rhizoctonia solani)、ごま葉枯病(Cochliobolus miyabeanus)、馬鹿苗病(Gibberella fujikuroi)；ムギ類のうどんこ病(Erysiphe graminis f.sp.hordei; f.sp.tritici)、さび病(Puccinia striiformis; P. graminis; P.recondita; P.hordei)、斑葉病(Pyrenophora graminea)、網斑病(Pyrenophora teres)、赤かび病(Gibberella zeae)、雪腐病(Typhula sp.; Micronectriella nivalis)、裸黒穂病(Ustilago tritici; U.nuda)、なまぐさ黒穂病(Tilletia caries)、眼紋病(Pseudocercosporella herpotrichoides)、株腐病(Rhizoctonia cerealis)、雲形病(Rhynchosporium secalis)、葉枯病(Septoria tritici)、ふ枯病(Leptosphaeria nodorum)；インゲン、キュウリ、トマト、イチゴ、ブドウ、ジャガイモ、ダイズ、キャベツ、ナス、レタス等の灰色かび病(Botrytis cinerea)；ブドウのべと病(Plasmopora viticola)、さび病(Phakopsora ampelopsidis)、うどんこ病(Uncinula necator)、黒とう病(Elsinoe ampelina)、晩腐病(Glomerella cingulata)；リンゴのうどんこ病(Podosphaera leucotricha)、黒星病(Venturia inaequalis)、斑点落葉病(Alternaria mali)、赤星病(Gymnosporangium yamadae)、モニリア病(Sclerotinia mali)、腐らん病(Valsa mali)；ナシの黒斑病(Alternaria kikuchiana)、黒星病(Venturia nashicola)、赤星病(Gymnosporangium haraeanum)、輪紋病(Physalospora piricola)；モモの灰星病(Sclerotinia cinerea)、黒星病(Cladosporium carpophilum)、フォモプシス腐敗病(Phomopsis sp.)；カキの炭そ病(Gloeosporium kaki)、落葉病(Cercospora kaki; Mycosphaerella nawae)、うどんこ病(Phyllactinia kakikora)；キュウリのべと病(Pseudoperonospora cubensis)、ウリ類のうどんこ病(Sphaerotheca fuliginea)、炭そ病(Colletotrichum lagenarium)、つる枯病(Mycosphaerella melonis)；トマトの輪紋病(Alternaria solani)、葉かび病(Cladosporium fulvam)、疫病(Phytophthora infestans)；ナスのうどんこ病(Erysiphe cichoracorum)、すすかび病(Mycovellosiella nattrassii)； アブラナ科野菜の黒斑病(Alternaria japonica)、白斑病(Cercosporella brassicae)；ネギのさび病(Puccinia allii)、黒斑病(Alternaria porri)； ダイズの紫斑病(Cercospora kikukuchii)、黒とう病(Elsinoe glycinnes)、黒点病(Diaporthe phaseololum)；インゲンの炭そ病(Colletotrichum lindemuthianum)；ラッカセイの黒渋病(Mycosphaerella personatum)、褐斑病(Cercospora arachidicola)；エンドウのうどんこ病(Erysiphe pisi)、べと病(Peronospora pisi)；ジャガイモの夏疫病(Alternaria solani)、黒あざ病(Rhizoctonia solani)、疫病(Phytophthora infestans)；ソラマメのべと病(Peronospora viciae)、疫病(Phytophthora nicotianae)；チャの網もち病(Exobasidium reticulatum)、白星病(Elsinoe leucospila)、炭そ病(Colletotrichum theae-sinensis) ；タバコの赤星病(Alternaria longipes)、うどんこ病(Erysiphe cichoracearum)、 炭そ病(Colletotrichum tabacum)、疫病(Phytophthora parasitica)；テンサイの褐斑病(Cercospora beticola)； バラの黒星病(Diplocarpon rosae)、うどんこ病(Sphaerotheca pannosa)、疫病(Phytophthora megasperma)； キクの褐斑病(Septoria chrysanthemi-indici)、白さび病(Puccinia horiana)；イチゴのうどんこ病(Sphaerotheca humuli)、疫病(Phytophthora nicotianae)；インゲン、キュウリ、トマト、イチゴ、ブドウ、ジャガイモ、ダイズ、キャベツ、ナス、レタス等の菌核病(Sclerotinia sclerotiorum)；カンキツの黒点病(Diaporthe citri)； ニンジンの黒葉枯病(Alternaria dauci) 等。なかでも、灰色かび病等に対して相乗的に増強された効果を有する。このような増強作用は、個々の有効成分の作用の合計からは予期されることではなかった。
【００１３】
本発明の殺菌剤組成物において、成分Ｉの置換チオフェン誘導体と成分ＩＩのフルジオキソニル、アニリノピリミジン系化合物、フルアジナム、イミノクタジン アルベシル酸塩またはポリオキシンの混合割合は特に限定されないが、通常、成分Ｉの化合物１重量部に対して成分ＩＩの化合物は０．０１〜５０重量部、好ましくは０．０１〜１０重量部、より好ましくは０．０２〜５重量部の範囲内である。
【００１４】
本組成物は、２種の有効成分を含む混合物を直接施用しても良いし、個々の有効成分を別々に同時施用するか、または相前後して施用しても良い。更に、有効成分を含む混合物は、２種の有効成分を含む濃厚組成物を水で希釈しても良いし、また、個々の有効成分を含む２種の濃厚液から使用時に混合物を調製し、これを水で希釈しても良い（タンクミックス法）。 本発明組成物を植物病害防除剤として使用する場合は、処理する植物に対して原体をそのまま使用してもよいが、一般には不活性な液体担体、固体担体、界面活性剤と混合し、通常用いられる製剤形態である粉剤、水和剤、フロアブル剤、乳剤、粒剤およびその他の一般に慣用される形態の製剤として使用される。更に製剤上必要ならば補助剤を添加することもできる。
【００１５】
ここでいう担体とは、処理すべき部位への有効成分の到達を助け、また有効成分化合物の貯蔵、輸送、取扱いを容易にするために配合される合成または天然の無機または有機物質を意味する。担体としては、通常農園芸用薬剤に使用されるものであるならば固体または液体のいずれでも使用でき、特定のものに限定されるものではない。
【００１６】
例えば、固体担体としては、モンモリロナイト、カオリナイト等の粘土類；珪藻土、白土、タルク、バ−ミュキュライト、石膏、炭酸カルシウム、シリカゲル、硫安等の無機物質；大豆粉、鋸屑、小麦粉等の植物性有機物質および尿素等が挙げられる。物性を改良するために、高分散ケイ酸または高分散吸収性ポリマーを添加することも可能である。
【００１７】
液体担体としては、トルエン、キシレン、クメン等の芳香族炭化水素類；ケロシン、鉱油などのパラフィン系炭化水素類；アセトン、メチルエチルケトン、シクロヘキサノンなどのケトン類；ジオキサン、ジエチレングリコールジメチルエーテルなどのエーテル類；メタノール、エタノール、プロパノール、エチレングリコールなどのアルコール類；ジメチルホルムアミド、ジメチルスルホキシドなどの非プロトン性溶媒および水等が挙げられる。
【００１８】
更に、製剤の剤型、適用場面等を考慮して目的に応じてそれぞれ単独に、または組み合わせて次の様な補助剤を添加することができる。補助剤としては、通常使用される界面活性剤、結合剤（例えば、リグニンスルホン酸、アルギン酸、ポリビニルアルコール、アラビアゴム、ＣＭＣナトリウム等）、安定剤（例えば、酸化防止用としてフェノール系化合物、チオール系化合物または高級脂肪酸エステル等を用いたり、ｐＨ調整剤として燐酸塩を用いたり、時に光安定剤も用いる）等を必要に応じて単独または組み合わせて使用できる。更に場合によっては防菌防黴のために工業用殺菌剤、防菌防黴剤などを添加することもできる。
【００１９】
補助剤について更に詳しく述べる。補助剤としては乳化、分散、拡展、湿潤、結合、安定化等の目的ではリグニンスルホン酸塩、アルキルベンゼンスルホン酸塩、アルキル硫酸エステル塩、ポリオキシアルキレンアルキル硫酸塩、ポリオキシアルキレンアルキルリン酸エステル塩等のアニオン性界面活性剤；ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルキルアリールエーテル、ポリオキシアルキレンアルキルアミン、ポリオキシアルキレンアルキルアミド、ポリオキシアルキレンアルキルアミド、ポリオキシアルキレンアルキルチオエーテル、ポリオキシアルキレン脂肪酸エステル、グリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシアルキレンソルビタン脂肪酸エステル、ポリオキシプロピレンポリオキシエチレンブロックポリマー等の非イオン性界面活性剤；ステアリン酸カルシウム、ワックス等の滑剤；イソプロピルヒドロジエンホスフェート等の安定剤；ホスファチジルエタノールアミン、ホスファチジルセリン、ホスファチジルグリセロール、リゾレシチン等のセファリンまたはレシチン系の天然または合成リン脂質；その他メチルセルロース、カルボキシメチルセルロース、カゼイン、アラビアゴム等が挙げられる。しかし、これらの成分は以上のものに限定されるものではない。
【００２０】
本発明組成物における有効成分組成物の含有量は、製剤形態によっても異なるが、通常粉剤では０．１〜３０重量％、水和剤では０．１〜８０重量％、粒剤では０．５〜２０重量％、乳剤では２〜５０重量％、フロアブル製剤では１〜５０重量％、ドライフロアブル製剤では１〜８０重量％であり、好ましくは、粉剤では０．５〜１０重量％、水和剤では５〜６０重量％、乳剤では５〜２０重量％、フロアブル製剤では５〜５０重量％およびドライフロアブル製剤では５〜５０重量％である。
【００２１】
補助剤の含有量は０〜８０重量％であり、担体の含有量は１００重量％から有効成分化合物のおよび補助剤の含有量を差し引いた量である。
【００２２】
本発明組成物の施用方法としては種子処理、茎葉散布、土壌灌注等が挙げられるが、通常当業者が利用するどの様な施用方法にても十分な効力を発揮する。施用量および施用濃度は対象作物、対象病害、病害の発生程度、化合物の剤型、施用方法および各種環境条件等によって変動するが、散布する場合には有効成分量としてヘクタール当たり５０〜２，０００ｇが適当であり、望ましくはヘクタール当り１００〜１、０００ｇである。また水和剤、フロアブル剤または乳剤を水で希釈して散布する場合、その希釈倍率は２００〜２０，０００倍が適当であり、望ましくは５００〜５，０００倍である。また、種子消毒の場合、殺菌剤混合物の使用量は、種子１ｋｇ当たり０．００１から５０ｇ、好ましくは０．０１から１０ｇである。
【００２３】
本発明の組成物は他の殺菌剤、殺虫剤、殺ダニ剤、殺線虫剤、除草剤および植物成長調節剤等の農薬、土壌改良剤または肥効物質との混合使用は勿論のこと、これらとの混合製剤も可能である。
【００２４】
次に、製剤例および試験例にて本発明を更に詳しく説明する。尚、製剤例中の部は重量部を表す。
【００２５】
【実施例】
製剤例 １（水和剤）
化合物番号１：１５部、フルジオキソニル：１０部、リグニンスルホン酸ナトリウム：１０部、アルキルナフタレンスルホン酸ナトリウム：５部、ホワイトカーボン：１０部および珪藻土：５０部を均一に粉砕混合して水和剤を得た。
【００２６】
製剤例 ２（水和剤）
化合物番号２：２０部、メパニピリム：２０部、リグニンスルホン酸ナトリウム：１部、アルキルベンゼンスルホン酸ナトリウム：２部および珪藻土：５７部を粉砕混合して、水和剤を得た。
【００２７】
製剤例 ３（水和剤）
化合物番号２：１５部、イミノクタジン アルベシル酸塩：３０部、リグニンスルホン酸ナトリウム：１部、アルキルベンゼンスルホン酸ナトリウム：２部および珪藻土：５２部を粉砕混合して、水和剤を得た。
【００２８】
製剤例 ４（フロアブル剤）
化合物番号３：１５部、フルアジナム：３０部、プロピレングリコール：３部、リグニンスルホン酸ナトリウム：２部、ジオクチルスルホサクシネートナトリウム塩：１部、および水：４９部をサンドグラインダーで湿式粉砕しフロアブル剤を得た。
【００２９】
製剤例 ５（水和剤）
化合物番号３：２０部、フルジオキソニル：２０部、リグニンスルホン酸カルシウム：３部、ラウリル硫酸ナトリウム：２部および珪藻土：５５部を粉砕混合して、水和剤を得た。
【００３０】
製剤例 ７（フロアブル剤）
化合物番号２：２０部、イミノクタジン アルベシル酸塩：３０部、プロピレングリコール：３部、リグニンスルホン酸ナトリウム：２部、ジオクチルスルホサクシネートナトリウム塩：１部、および水：４４部をサンドグラインダーで湿式粉砕しフロアブル剤を得た。
【００３１】
製剤例 ８（フロアブル剤）
化合物番号２：２５部、メパニピリム：２０部、ポリオキシエチレンソルビタンモノオレエート：３部、カルボキシメチルセルロ−ス：３部および水：４９部をサンドグラインダーで湿式粉砕しフロアブル剤を得た。
【００３２】
次に本発明化合物の農園芸用殺菌剤としての効力を試験例によって説明する。
【００３３】
試験例１ インゲン灰色かび病防除試験（１）
温室内で直径７．５ｃｍのプラスチックポットに子葉の展開まで２本ずつ生育させたインゲン（品種：つるなしトップクロップ）に、製剤例１に準じて調製した水和剤を所定濃度に希釈して、４ポット当たり５０ｍｌずつ散布した。薬液が乾いた後ＰＤＡ培地上で培養した灰色かび菌（ＭＢＣ耐性、ＲＳ菌）から調製した分生胞子懸濁液（１×１０⁵個／ｍｌ）を子葉上に噴霧接種し、２０〜２３℃、湿度９５％以上の温室に７日間保った。接種７日後、インゲン１葉当たりに灰色かび病の病斑が占める面積を次の指標に従って調査した。結果を第１表（表１，２）に示す。
【００３４】

【００３５】
防除価（％）＝（１−処理区の発病度／無処理区の発病度）×１００
【００３６】
【表１】

【００３７】
【表２】

【００３８】
【発明の効果】
本発明は、少なくとも２種の有効成分を含む殺菌剤組成物であり、広範囲の植物病害、特に灰色かび病に対して相乗的に増強された効果を示すことから、植物病害防除剤組成物として有用である。
【００３９】
このような本発明の組成物を使用することにより、慣用の方法に比べて予期しない少量の有効成分量で、病害の防除ができる。[0001]
BACKGROUND OF THE INVENTION
The present invention is a plant protection composition having at least two active ingredients and having a synergistically enhanced effect against disease infection. More specifically, one of the active ingredients is a substituted thiophene derivative showing a plant disease control action, and the other is at least one of compounds selected from fludioxonil, anilinopyrimidine compounds, fluazinam, iminoctadine albecylate or polyoxin. It is related with the disinfectant composition to contain.
[0002]
[Prior art]
Unlike the non-selective fungicides that have been used so far, fungicides that have been developed in recent years show stable effects at low doses. There is a risk of lowering. As countermeasures, mixing with prophylactic agents, mixing with drugs with different mechanisms of action, or limiting the number of uses of the drugs themselves, and the development of new drugs are expected.
[0003]
JP-A-9-235282 (European Patent Publication No. 7376682) discloses that a new substituted thiophene derivative represented by Component I has a bactericidal effect against various diseases. This compound exhibits a preventive and therapeutic control effect against infections of various diseases including gray mold and powdery mildew.
[0004]
On the other hand, Component II is a known compound selected from fludioxonil, anilinopyrimidine compounds, fluazinam, iminoctadine albecylate or polyoxin, and is represented by the following generic name ["trade name (English name)", page] Refers to the description page of [The Pesticide Manual, 11th edition, The British Crop Protection Council, 1997].
A. Anilinopyrimidine compounds Pyrimethanyl ["Scala", pp. 1068-1069]
2. Mepanipyrim [“Frupica”, pp. 784-785]
3. Cyprodinil ["Unix", pp. 319-321]
B. Other 4. Fludioxonil ["Saphire", pp. 566-568]
5). Full azinam ["Fronside", pp. 558-559]
6). Iminoctadine albesylate ["Bellekute", pp. 709-712]
7). Polyoxin ["Polyoxin AL", pp. 991-994]
For example, anilinopyrimidine-based fungicides are effective against gray mold and powdery mildew, but have poor residual effect and powdery mildew. Iminotazine arbesylate is also effective against gray mold and powdery mildew, but is less effective and higher in dosage. Fludioxonil is effective against gray mold at low doses but has a narrow bactericidal spectrum. Polyoxins are effective against gray mold and powdery mildew, but their residual effects are short, causing stains when sprayed just before harvesting grapes, and recently, resistant bacteria have become a problem. Crops are infected with various diseases, and in order to control the crops, it is preferable to expand the sterilization spectrum. Further, in view of the fear of resistant bacteria and the burden on the environment, it is desirable to reduce the amount used.
[0005]
[Problems to be solved by the invention]
Accordingly, the present invention contains at least two active ingredients of one of the thiophene derivatives of Component I and one of Component II fludioxonil, anilinopyrimidine compounds, fluazinam, iminoctazine albesylate or polyoxin, and synergistically. An object of the present invention is to provide a plant disease control agent composition having an enhanced action and to reduce the amount of drug used.
[0006]
[Means for Solving the Problems]
As a result of various studies to solve the above problems, the present inventors have surprisingly found that at least one of component fludioxonil, anilinopyrimidine-based compound, fluazinam, iminoctadine albesylate or polyoxin and component I That the composition mixed with one of the thiophene derivatives of the present invention exhibits an enhanced synergistic effect on the infection of a wide range of plant diseases, in particular diseases such as gray mold disease, and is therefore suitable for solving the above problems. The headline and the present invention were completed.
[0007]
That is, the present invention is a plant protection composition having at least two active ingredients and having a synergistic effect on disease infection.
[0008]
[Chemical 3]

[Wherein Q is a hydrogen atom, a methyl group, a trifluoromethyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, a methylthio group, a methylsulfoxy group, a methylsulfonyl group, a cyano group, an acetyl group, A nitro group, an alkoxycarbonyl group or an amino group, wherein R represents a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched halogenoalkyl group having 1 to 12 carbon atoms, or a straight chain having 2 to 10 carbon atoms. Chain or branched alkenyl group, linear or branched halogenoalkenyl group having 2 to 10 carbon atoms, alkylthioalkyl group having 2 to 10 carbon atoms, alkyloxyalkyl group having 2 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms A cycloalkyl group having 3 to 10 carbon atoms which may be substituted with a group, a halogen atom having 3 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms A substituted cycloalkyl group, or a phenyl group optionally substituted by 1 to 3 substituents, and the substituent of the phenyl group is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group having 2 to 4 carbon atoms. An alkenyl group, an alkynyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogenoalkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, An alkylsulfoxy group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, an acyl group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, an amino group, or An amino group substituted with an alkyl group having 1 to 3 carbon atoms, R and —NHCOAr are adjacent to each other, and Ar is represented by the following (A1) to (A8) (Chemical Formula 4)
[0009]
[Formula 4]

(Wherein R1 is a trifluoromethyl group, difluoromethyl group, methyl group, ethyl group, chlorine atom, bromine atom or iodine atom, R2 is a hydrogen atom, methyl group, trifluoromethyl group or amino group; n is an integer of 0 to 2)], and the component II is selected from fludioxonil, anilinopyrimidine-based compounds, fluazinam, iminoctadine albesylate or polyoxin It relates to a composition containing at least one.
[0010]
By using the composition of the present invention, it is possible to effectively control diseases with an amount of active ingredient that is unexpectedly small compared to conventional methods. In addition to the synergistic effect on gray mold, this drug is highly advantageous in that it also shows high effects on powdery mildew, red rust, and the like.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Of the compounds represented by the component I of the present invention, preferred is a Ar is (A1), R1 is CF ₃ or Me group, R2 is Me group; in the Ar (A2), R1 is CF ₃ Or CHF ₂ group; Ar is (A3), R1 is Me group, R2 is hydrogen atom or Me group; Ar is (A4), R1 is Me group, n is 0 to 1; Ar is ( A5), R1 is a chlorine atom; Ar is (A6) or (A7); Ar is (A8), R1 is a Me group, and R is a linear or branched alkyl group having 4 to 8 carbon atoms; Or it is a compound represented by the C4-C8 cycloalkyl group which may be substituted by the C1-C4 alkyl group. Particularly preferred are, Ar in the (A1), R1 is CF ₃ or Me group, R2 is Me group; a is Ar (A2), R1 is CF ₃ or CHF ₂ group, R3 is a hydrogen atom And R is a compound represented by a linear or branched alkyl group having 4 to 8 carbon atoms or a cycloalkyl group having 4 to 8 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms. .
[0012]
The following are some specific examples of the compound represented by Component I.
Compound No. 1: N- {2- (1,3-dimethylbutyl) -3-thienyl} -2,4-dimethylthiazole-5-carboxylic acid amide
[When R is 1,3-dimethylbutyl group and Ar is A1 (R1 = Me, R2 = Me)]
Compound No. 2: N- {2- (1,3-dimethylbutyl) -3-thienyl} -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide
[When R is 1,3-dimethylbutyl group and Ar is A2 (R1 = CF ₃ )]
Compound No. 3: N- {2- (1,3-dimethylbutyl) -3-thienyl} -2-methylfuran-3-carboxylic acid amide
[When R is 1,3-dimethylbutyl group and Ar is A3 (R1 = Me, R2 = H)]
Compound No. 4: N- {2- (1,3-dimethylbutyl) -3-thienyl} -3-methylthiophene-2-carboxylic acid amide
[When R is 1,3-dimethylbutyl group and Ar is A4 (R1 = Me, n = 0)]
Compound No. 5: N- {2- (1,3-dimethylbutyl) -3-thienyl} -2-chloronicotinic acid amide
[When R is 1,3-dimethylbutyl group and Ar is A6]
The composition of the present invention is effective against the following types of plant diseases: rice blast ( Pyricularia oryzae ), blight ( Rhizoctonia solani ), sesame leaf blight ( Cochliobolus miyabeanus ), idiotic seedling ( Gibberella fujikuroi); wheat powdery mildew (Erysiphe graminis f.sp. hordei; f.sp. tritici ), rusts (Puccinia striiformis; P graminis;. P recondita;.. P hordei), Madarahabyo (Pyrenophora graminea ), net blotch (Pyrenophora teres ), red mold ( Gibberella zeae ), snow rot ( Typhula sp .; Micronectriella nivalis ), naked smut ( Ustilago tritic i; U. nuda ), Tunatia caries ( Tilletia caries) ), Eye spot disease ( Pseudocercosporella herpotrichoides ), strain rot ( Rhizoctonia cerealis ), cloud disease ( Rhynchosporium secalis ), leaf blight ( Septoria tritici ), blight ( Leptosphaeria nodorum ); green beans, cucumbers, tomatoes, strawberries, grapes , Gray mold (potato, soybean, cabbage, eggplant, lettuce, etc.) Botrytis cinerea ); grape downy mildew ( Plasmopora viticola ), rust ( Phakopsora ampelopsidis ), powdery mildew ( Uncinula necator ), black mildew ( Elsinoe ampelina ), late rot ( Glomerella cingulata ); apple powdery mildew ( Podosphaera leucotricha ), black spot disease ( Venturia inaequalis ), spotted leaf disease ( Alternaria mali ), red star disease ( Gymnosporangium yamadae ), moniliosis ( Sclerotinia mali ), rot ( Valsa mali ); pear black spot disease ( Alternaria kiku , Black streak ( Venturia nashicola ), red streak ( Gymnosporangium haraeanum ), ring rot ( Physalospora piricola ); peach blight ( Sclerotinia cinerea ), black streak ( Cladosporium carpophilum ), fomopsis rot ( Phomopsis sp.); Anthracnose ( Gloeosporium kaki ), deciduous leaf ( Cercospora kaki ; Mycosphaerella nawae ), powdery mildew ( Phyllactinia kakikora ); cucumber downy mildew ( Pseudoperonospora cubensis ), cucumber powdery mildew ( Sphaerotheca fuliginea ) disease ( Colletotrichum lagenarium ), vine blight ( Mycosphaerella melonis ); tomato ring-rot ( Alternaria solani ), leaf mold ( Cladosporium fulvam ), plague ( Phytophthora infestans ); eggplant powdery mildew ( Erysiphe cichoracorum ) ( Mycovellosiella nattrassii ); cruciferous vegetable black spot ( Alternaria japonica ), white spot ( Cercosporella brassicae ); green onion rust ( Puccinia allii ), black spot ( Alternaria porri ); soybean purpura ( Cercospora kikukuchii ), Black pepper ( Elsinoe glycinnes ), black spot ( Diaporthe phaseololum ); beans anthracnose ( Colletotrichum lindemuthianum ); groundnut black astringency ( Mycosphaerella personatum ); brown spot ( Cercospora arachidicola ); pea powdery mildew ( Ery pisi), downy mildew (Peronospora pisi); early blight of potatoes (Alternaria solani), black bruises disease (Rhizoctonia solani), late blight (Phytophthora infestans); broad bean of downy mildew (Peronospora viciae), disease (Phytophthora nicotianae); tea of the network have disease (Exobasidium reticulatum), white star disease (Elsinoe leucospila), anthracnose (Colletotrichum theae-sinensis); tobacco gymnosporangium (Alternaria longipes), powdery mildew (Erysiphe cichoracearum), charcoal Colletotrichum tabacum , plague ( Phytophthora parasitica ); brown spot of sugar beet ( Cercospora beticola ); black spot of rose ( Diplocarpon rosae ), powdery mildew ( Sphaerotheca pannosa ), plague ( Phytophthora megasperma ); Disease ( Septoria chrysanthemi - indici ), white rust ( Puccinia horiana ); strawberry powdery mildew ( Sphaerotheca humuli ), plague ( Phytophthora nicotianae ); kidney beans, cucumber, tomato, strawberry, grape, potato, soybean, cabbage, eggplant, Sclerotia disease such as lettuce (S clerotinia sclerotiorum ); Black spot disease of citrus ( Diaporthe citri ); Black leaf blight of carrot ( Alternaria dauci ) and the like. Among them, it has a synergistically enhanced effect against gray mold disease and the like. Such a potentiating effect was not expected from the sum of the effects of the individual active ingredients.
[0013]
In the fungicide composition of the present invention, the mixing ratio of the component I substituted thiophene derivative and the component II fludioxonil, anilinopyrimidine compound, fluazinam, iminoctadine albecylate or polyoxin is not particularly limited. The compound of component II is in the range of 0.01 to 50 parts by weight, preferably 0.01 to 10 parts by weight, more preferably 0.02 to 5 parts by weight with respect to 1 part by weight.
[0014]
The present composition may be applied directly as a mixture containing two active ingredients, or may be applied separately or simultaneously with each active ingredient separately. Further, the mixture containing the active ingredients may be diluted with a concentrated composition containing the two active ingredients with water, or prepared from two concentrates containing the individual active ingredients at the time of use, This may be diluted with water (tank mix method). When the composition of the present invention is used as a plant disease control agent, the active ingredient may be used as it is for the plant to be treated, but generally mixed with an inert liquid carrier, solid carrier, surfactant, It is used as powders, wettable powders, flowables, emulsions, granules and other commonly used forms of preparations that are commonly used preparation forms. Further, auxiliary agents can be added if necessary for the preparation.
[0015]
Carrier as used herein means a synthetic or natural inorganic or organic substance formulated to help the active ingredient reach the site to be treated and to facilitate the storage, transport and handling of the active ingredient compound. . As the carrier, any solid or liquid can be used as long as it is usually used for agricultural and horticultural chemicals, and it is not limited to a specific one.
[0016]
For example, solid carriers include clays such as montmorillonite and kaolinite; inorganic substances such as diatomaceous earth, white clay, talc, vermiculite, gypsum, calcium carbonate, silica gel, and ammonium sulfate; plant organics such as soybean flour, sawdust, and wheat flour Examples include substances and urea. In order to improve the physical properties, it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers.
[0017]
Examples of liquid carriers include aromatic hydrocarbons such as toluene, xylene and cumene; paraffinic hydrocarbons such as kerosene and mineral oil; ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as dioxane and diethylene glycol dimethyl ether; methanol, Examples include alcohols such as ethanol, propanol, and ethylene glycol; aprotic solvents such as dimethylformamide and dimethyl sulfoxide, and water.
[0018]
Furthermore, the following adjuvants can be added singly or in combination depending on the purpose in consideration of the dosage form of the preparation, application scene, and the like. Adjuvants include commonly used surfactants, binders (for example, lignin sulfonic acid, alginic acid, polyvinyl alcohol, gum arabic, sodium CMC, etc.), stabilizers (for example, phenolic compounds and thiols for antioxidant purposes). Compounds, higher fatty acid esters, etc., phosphates as pH adjusters, and sometimes light stabilizers) may be used alone or in combination as required. Further, in some cases, an industrial disinfectant, an antibacterial / antifungal agent, or the like may be added for antibacterial / antifungal purposes.
[0019]
The adjuvant will be described in more detail. Adjuvants include lignin sulfonates, alkylbenzene sulfonates, alkyl sulfate esters, polyoxyalkylene alkyl sulfates, polyoxyalkylene alkyl phosphate esters for purposes such as emulsification, dispersion, spreading, wetting, bonding, and stabilization. Anionic surfactants such as salts; polyoxyalkylene alkyl ether, polyoxyalkylene alkyl aryl ether, polyoxyalkylene alkyl amine, polyoxyalkylene alkyl amide, polyoxyalkylene alkyl amide, polyoxyalkylene alkyl thioether, polyoxyalkylene fatty acid Esters, glycerin fatty acid esters, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxypropylene polyoxyethylene block polymers Nonionic surfactants; Lubricants such as calcium stearate and wax; Stabilizers such as isopropylhydrodiene phosphate; Sephaline or lecithin-based natural or synthetic phospholipids such as phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, and lysolecithin; Examples include methyl cellulose, carboxymethyl cellulose, casein, and gum arabic. However, these components are not limited to the above.
[0020]
The content of the active ingredient composition in the composition of the present invention varies depending on the preparation form, but is usually 0.1 to 30% by weight for powders, 0.1 to 80% by weight for wettable powders, and 0.5 for granules. -20 wt%, emulsion 2-50 wt%, flowable formulation 1-50 wt%, dry flowable formulation 1-80 wt%, preferably 0.5-10 wt% powder, wettable powder 5 to 60% by weight, 5 to 20% by weight for emulsions, 5 to 50% by weight for flowable formulations, and 5 to 50% by weight for dry flowable formulations.
[0021]
The content of the adjuvant is 0 to 80% by weight, and the content of the carrier is an amount obtained by subtracting the content of the active ingredient compound and the adjuvant from 100% by weight.
[0022]
Examples of the application method of the composition of the present invention include seed treatment, foliage spraying, soil irrigation and the like, and any application method usually used by those skilled in the art exhibits sufficient efficacy. The application rate and application concentration vary depending on the target crop, target disease, degree of disease occurrence, compound dosage form, application method and various environmental conditions, but when sprayed, the active ingredient amount is 50 to 2,000 g per hectare. Is preferably 100 to 1,000 g per hectare. In addition, when the wettable powder, flowable preparation or emulsion is diluted with water and sprayed, the dilution ratio is suitably 200 to 20,000 times, preferably 500 to 5,000 times. In the case of seed disinfection, the amount of the fungicide mixture used is 0.001 to 50 g, preferably 0.01 to 10 g, per 1 kg of seed.
[0023]
The composition of the present invention can be used in combination with other fungicides, insecticides, acaricides, nematicides, herbicides, plant growth regulators, and other agricultural chemicals, soil conditioners or fertilizers, Mixed preparations with these are also possible.
[0024]
Next, the present invention will be described in more detail with formulation examples and test examples. In addition, the part in a formulation example represents a weight part.
[0025]
【Example】
Formulation Example 1 (wettable powder)
Compound No. 1: 15 parts, fludioxonil: 10 parts, sodium lignin sulfonate: 10 parts, sodium alkylnaphthalene sulfonate: 5 parts, white carbon: 10 parts and diatomaceous earth: 50 parts are uniformly ground and mixed to obtain a wettable powder. Obtained.
[0026]
Formulation Example 2 (wettable powder)
Compound No. 2: 20 parts, mepanipyrim: 20 parts, sodium lignin sulfonate: 1 part, sodium alkylbenzene sulfonate: 2 parts and diatomaceous earth: 57 parts were mixed to obtain a wettable powder.
[0027]
Formulation Example 3 (wettable powder)
Compound No. 2: 15 parts, iminotadine albesylate: 30 parts, sodium lignin sulfonate: 1 part, sodium alkylbenzenesulfonate: 2 parts and diatomaceous earth: 52 parts were mixed to obtain a wettable powder.
[0028]
Formulation Example 4 (Flowable)
Compound No. 3: 15 parts, fluazinam: 30 parts, propylene glycol: 3 parts, sodium lignin sulfonate: 2 parts, dioctyl sulfosuccinate sodium salt: 1 part, and water: 49 parts wet crushed with a sand grinder and a flowable agent Got.
[0029]
Formulation Example 5 (wettable powder)
Compound No. 3: 20 parts, fludioxonil: 20 parts, calcium lignin sulfonate: 3 parts, sodium lauryl sulfate: 2 parts and diatomaceous earth: 55 parts were mixed to obtain a wettable powder.
[0030]
Formulation Example 7 (Flowable)
Compound No. 2: 20 parts, iminotadine albesylate: 30 parts, propylene glycol: 3 parts, sodium lignin sulfonate: 2 parts, dioctyl sulfosuccinate sodium salt: 1 part, and water: 44 parts by wet grinding with a sand grinder The flowable agent was obtained.
[0031]
Formulation Example 8 (Flowable)
Compound No. 2: 25 parts, mepanipyrim: 20 parts, polyoxyethylene sorbitan monooleate: 3 parts, carboxymethyl cellulose: 3 parts and water: 49 parts were wet-ground with a sand grinder to obtain a flowable agent.
[0032]
Next, the effectiveness of the compounds of the present invention as agricultural and horticultural fungicides will be described with reference to test examples.
[0033]
Test Example 1 Green Bean Mold Control Test (1)
Into a green bean grown in a plastic pot with a diameter of 7.5 cm in a greenhouse until the development of cotyledons (variety: Tsurunashi Top Crop), a wettable powder prepared according to Formulation Example 1 was diluted to a predetermined concentration. 50 ml was sprayed per 4 pots. A conidial spore suspension (1 × 10 ⁵ cells / ml) prepared from gray mold (MBC resistant, RS bacterium) cultured on PDA medium after the drug solution is dried is spray-inoculated on cotyledons, and 20-23 It was kept in a greenhouse at 95 ° C. and a humidity of 95% or more for 7 days. Seven days after inoculation, the area occupied by the spots of gray mold per leaf of green beans was examined according to the following index. The results are shown in Table 1 (Tables 1 and 2).
[0034]

[0035]
Control value (%) = (1−Disease level in treated area / Disease level in untreated area) × 100
[0036]
[Table 1]

[0037]
[Table 2]

[0038]
【The invention's effect】
The present invention is a fungicide composition comprising at least two active ingredients and exhibits a synergistically enhanced effect on a wide range of plant diseases, particularly gray mold disease. Useful.
[0039]
By using such a composition of the present invention, it is possible to control diseases with an amount of active ingredient that is unexpectedly small compared to conventional methods.

Claims (6)

Contains at least two active ingredients of one of the following component I thiophene derivatives and one of component II fludioxonil, anilinopyrimidine compound, fluazinam, iminoctadine albesylate, and has a synergistic effect on disease infection A plant protection composition having the following component I:

[Wherein Q is a hydrogen atom, a methyl group, a trifluoromethyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, a methylthio group, a methylsulfoxy group, a methylsulfonyl group, a cyano group, an acetyl group, A nitro group, an alkoxycarbonyl group or an amino group, wherein R represents a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched halogenoalkyl group having 1 to 12 carbon atoms, or a straight chain having 2 to 10 carbon atoms. Chain or branched alkenyl group, linear or branched halogenoalkenyl group having 2 to 10 carbon atoms, alkylthioalkyl group having 2 to 10 carbon atoms, alkyloxyalkyl group having 2 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms A cycloalkyl group having 3 to 10 carbon atoms which may be substituted with a group, a halogen atom having 3 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms A substituted cycloalkyl group, or a phenyl group optionally substituted by 1 to 3 substituents, and the substituent of the phenyl group is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group having 2 to 4 carbon atoms. An alkenyl group, an alkynyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogenoalkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, An alkylsulfoxy group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, an acyl group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, an amino group, or An amino group substituted with an alkyl group having 1 to 3 carbon atoms, R and —NHCOAr are adjacent to each other, and Ar is the following (A1), (A2) or (A3) (Chemical Formula 2)

(Wherein R1 is a trifluoromethyl group, difluoromethyl group, methyl group, ethyl group, chlorine atom, bromine atom or iodine atom, R2 is a hydrogen atom, methyl group, trifluoromethyl group or amino group; n is an integer of 0 to 2)]. A composition which is a substituted thiophene derivative represented by:  In Component I, Q is a hydrogen atom, R is a linear or branched alkyl group having 3 to 10 carbon atoms, a linear or branched halogenoalkyl group having 3 to 10 carbon atoms, or a linear chain having 3 to 10 carbon atoms. Or a branched alkenyl group, a linear or branched halogenoalkenyl group having 3 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms. The composition according to 1. In component I, Ar is the (A1), R1 is CF ₃ or Me group The composition of claim 2 wherein R2 is Me group. In component I, Ar is is (A2), A composition according to claim 2, wherein R1 is CF ₃ or CHF ₂ group. The composition according to claim 2, 3 or 4, wherein, in Component II, the anilinopyrimidine compound is pyrimethanil, mepanipyrim, or cyprodinil. 5. A composition according to claim 2, 3 or 4 wherein component II is fludioxonil, fluazinam or iminotadine arbesylate .