JP4526622B2 - Agricultural / horticultural seed disinfectant and seed disinfecting method - Google Patents

Description

【００１３】
[式[I]中、Ｒ¹、Ｒ²はそれぞれアミノ酸の側鎖を示し、これらは互いに同一でも異なっていてもよく、Ｍは、銅、亜鉛、マンガン、鉄およびマグネシウムのうちの何れかを示す。]
本発明においては、上記式[I]中、Ｒ¹、Ｒ²が同一であって、これらが中性アミノ酸側鎖、塩基性アミノ酸側鎖、酸性アミノ酸側鎖の何れかであってもよい。本発明においては、上記式[I]中、Ｒ¹が塩基性アミノ酸側鎖であり、Ｒ²が酸性アミノ酸側鎖であってもよい。
【００１４】
本発明に係る農園芸用種子消毒剤は、
(i)塩基性、中性または酸性アミノ酸あるいはその塩と、
(ii)金属あるいは無機金属化合物と、
を有効成分として含有していることを特徴としている。
本発明に係る種子の消毒方法は、金属あるいは無機金属化合物を有効成分として含有する農園芸用殺菌剤と、水と、塩基性、中性または酸性アミノ酸あるいはその塩とを同時に、あるいは任意の順序で配合してなる種子消毒剤、好ましくは上記農園芸用殺菌剤に水と、上記アミノ酸あるいはその塩とを配合してなる種子消毒液を用いて種子を消毒することを特徴としている。
【００１５】
本発明においては、上記何れの場合も、無機金属化合物が、金属亜酸化物、金属水酸化物、金属塩のうちの何れか１種以上であることが望ましい。
本発明においては、上記何れの場合も、金属あるいは無機金属化合物が、銅あるいは無機系銅化合物、例えば、亜酸化銅、硫酸銅、塩化銅、水酸化銅、塩基性塩化銅、塩基性硫酸銅であることが好ましい。
【００１６】
このような本発明に係る農園芸用種子消毒剤は、イネ種子をはじめとする種々の植物の種子に対して優れた種子消毒活性を有すると共に、作物や人畜に対する安全性も高い。
このような本発明に係る種子の消毒方法によれば、作物や人畜に対して安全で、しかも効率よく種子の消毒を行うことができる。
【００１７】
【発明の具体的説明】
以下、本発明に係る農園芸用種子消毒剤について具体的に説明する。
＜アミノ酸金属錯化合物類＞
本発明に係る農園芸用種子消毒剤には、殺菌性有効成分である次式[I]で表されるアミノ酸金属錯化合物あるいはその塩（アミノ酸金属錯化合物類）が含まれている。
【００１８】
【化３】

【００１９】
[式[I]中、Ｒ¹ 、Ｒ²はそれぞれアミノ酸の側鎖を示し、これらは互いに同一でも異なっていてもよく、Ｍは、銅、亜鉛、マンガン、鉄およびマグネシウムのうちの何れかを示す。]
上記アミノ酸側鎖Ｒ¹、Ｒ²としては、水素原子あるいは、炭素数が１〜１０、好ましくは１〜５、さらに好ましくは１〜３、特に好ましくは１〜２の直鎖状あるいは分岐状のアルキル基；水素原子の一部が水酸基にて置換された上記アルキル基（水酸基含有アルキル基）；上記アルキル基中の隣接するＨ−Ｃ間あるいはＣ−Ｃ間にＳ原子が介在した硫黄含有アルキル基；上記アルキル基中の水素原子の一部がカルボキシル基にて置換されたカルボキシル基含有アルキル基；同じくアミノ基にて置換されたアミノ基含有アルキル基；アミド基含有アルキル基；上記アルキル基中の水素原子の一部が芳香環にて置換された芳香環含有アルキル基；複素環含有アルキル基（あるいはアルキレン基）が挙げられる。但し、各種置換基含有アルキル基、アルキレン基におけるアルキル基等の炭素数は、何れも上記アルキル基の場合と同様である（以下同様）。
【００２０】
上記アミノ酸側鎖Ｒ¹、Ｒ²が水素原子、あるいはアルキル基の例としては、グリシン由来の水素原子、アラニン由来のＣＨ₃−、バリン由来の（ＣＨ₃）₂ＣＨ−、ロイシン由来の（ＣＨ₃）₂ＣＨＣＨ₂−、イソロイシン由来のＣ₂Ｈ₅ＣＨ（ＣＨ₃）−等が挙げられ、これらのうちでは、上記アミノ酸側鎖Ｒ¹、Ｒ²が水素原子、あるいは炭素数３以下さらには２以下のアルキル基であると、水溶性に優れ、種子消毒効果に優れるアミノ酸金属錯化合物類となるため好ましい。
【００２１】
水酸基含有アルキル基としては、例えば、セリン由来のＨＯＣＨ₂−、トレオニン由来のＣＨ₃ＣＨ（ＯＨ）-等が挙げられる。
上記硫黄含有アルキル基としては、例えば、システィン由来のＨＳＣＨ₂−、シスチン由来のＨＯＯＣ（ＮＨ₂）ＣＨＣＨ₂ＳＳＣＨ₂−、メチオニン由来のＣＨ₃Ｓ（ＣＨ₂）₂−等が挙げられる。
【００２２】
カルボキシル基含有アルキル基としては、酸性アミノ酸のアスパラギン酸由来のＨＯＯＣＣＨ₂−、酸性アミノ酸のグルタミン酸由来のＨＯＯＣ（ＣＨ₂）₂−等が挙げられる。
アミノ基含有アルキル基（アミド基を有するものを除き、水酸基とアミノ基の両者を有するもの、アミノ基とＳ原子を有するもの、およびグアニジル基を有するものを含む。）としては、塩基性アミノ酸のリジン（Lysine）由来のＨ₂Ｎ（ＣＨ₂）₄−、塩基性アミノ酸のアルギニン由来のＨ₂ＮＣ（＝ＮＨ）ＮＨ（ＣＨ₂）₃−、オルニチン由来のＨ₂Ｎ（ＣＨ₂）₃−、ヒドロキシリジン由来のＨ₂ＮＣＨ₂ＣＨ（ＯＨ）（ＣＨ₂）₂−、チアリジン由来のＨ₂Ｎ（ＣＨ₂）ＳＣＨ₂−、ジアミノブチル酸由来のＨ₂Ｎ（ＣＨ₂）₂−、ジアミノプロピオン酸由来のＨ₂ＮＣＨ₂−等が挙げられる。
【００２３】
アミド基含有アルキル基としては、グルタミン由来のＨ₂ＮＣＯ（ＣＨ₂）₂−、アスパラギン由来のＨ₂ＮＣＯＣＨ₂−等が挙げられる。
芳香環含有アルキル基としては、フェニルアラニン由来のＰｈ-ＣＨ₂−（但し、Ｐｈ：フェニル基）、チロシン由来のＨＯ−Ｐｈｅ−ＣＨ₂−（但し、Ｐｈｅ：フェニレン基）等が挙げられる。
【００２４】
複素環含有アルキル基（あるいはアルキレン基）としては、塩基性アミノ酸のヒスチジン由来のＩｍｉ−ＣＨ₂−（但し、Ｉｍｉ：イミダゾール環）、トリプトファン由来のＩｎｄｏ−ＣＨ₂−（但し、Ｉｎｄｏ：インドール環）、プロリン由来の−（ＣＨ₂）₃−、オキシプロリン由来の−ＣＨ₂ＣＨ（ＯＨ）ＣＨ₂−等が挙げられる。
【００２５】
上述したようなＲ¹、Ｒ²のうちでは、水溶性に優れ、種子消毒効果に優れたアミノ酸金属錯化合物が得られる点で、Ｒ¹、Ｒ²が、水素原子、炭素数３以下、さらには２以下のアルキル基；水酸基含有アルキル基；カルボキシル基含有アルキル基；アミノ基含有アルキル基（アミド基を有するものを除き、水酸基とアミノ基の両者を有するもの、アミノ基とＳ原子を有するもの、およびグアニジル基を有するものを含む。）；アミド基含有アルキル基；芳香環含有アルキル基のうちのチロシン由来のＨＯ-Ｐｈ−ＣＨ₂−（但し、Ｐｈ：フェニレン基）；複素環含有アルキル基（あるいはアルキレン基）のうちのヒスチジン由来のＩｍｉ−ＣＨ₂−（但し、Ｉｍｉ：イミダゾール環）、プロリン由来の−（ＣＨ₂）₃−、ヒドロキシプロリン由来の−ＣＨ₂ＣＨ（ＯＨ）ＣＨ₂−が好ましい。
【００２６】
これらのうちでも、アミノ酸側鎖Ｒ¹、Ｒ²としては、特に、グリシン由来の水素原子、アラニン由来のＣＨ₃−、セリン由来のＨＯＣＨ₂−、リジン（Lysine）由来のＨ₂Ｎ（ＣＨ₂）₄−、アルギニン由来のＨ₂ＮＣ（＝ＮＨ）ＮＨ（ＣＨ₂）₃−、オルニチン由来のＨ₂Ｎ（ＣＨ₂）₃−、ヒドロキシリジン由来のＨ₂ＮＣＨ₂ＣＨ（ＯＨ）ＣＨ₂ＣＨ₂−、チアリジン由来のＨ₂Ｎ（ＣＨ₂）ＳＣＨ₂−、ジアミノブチル酸由来のＨ₂Ｎ（ＣＨ₂）₂−、ジアミノプロピオン酸由来のＨ₂ＮＣＨ₂−、ヒドロキシプロリン由来の−ＣＨ₂ＣＨ（ＯＨ）ＣＨ₂−が好ましい。
【００２７】
このようなアミノ酸金属錯化合物[I]としては、具体的には、例えば、表１にまとめて示すように、上記式[I]中、Ｒ¹、Ｒ²が共にアスパラギン側鎖（Ｈ₂ＮＣＯ−ＣＨ₂−）であり、Ｍが銅であるビス−Ｌ-アスパラギン銅錯化合物（化合物Ｎｏ．１）、
Ｒ¹、Ｒ²が共にアラニン側鎖（ＣＨ₃−）であり、Ｍが銅であるビス−Ｌ-アラニン銅錯化合物（化合物Ｎｏ．２）あるいはビス−β-アラニン銅錯体（化合物Ｎｏ．３）、
Ｒ¹、Ｒ²がイソロイシン側鎖（Ｃ₂Ｈ₅ＣＨ（ＣＨ₃）−）であり、Ｍが銅であるビス−Ｌ-イソロイシン銅錯化合物（化合物Ｎｏ．５）、
Ｒ¹、Ｒ²がグリシン側鎖（Ｈ）であり、Ｍが銅であるビス−グリシン銅錯化合物（化合物Ｎｏ．７）、
Ｒ¹、Ｒ²が共にグルタミン側鎖（Ｈ₂Ｎ（ＣＯ）−（ＣＨ₂）₂−）であり、Ｍが銅であるビス−Ｌ-グルタミン銅錯化合物（化合物Ｎｏ．８）、
Ｒ¹、Ｒ²が共にセリン側鎖（ＨＯＣＨ₂−）であり、Ｍが銅であるビス−Ｌ-セリン銅錯化合物（化合物Ｎｏ．１１）、
Ｒ¹、Ｒ²が共にトリプトファン側鎖[Ｉｎｄｏ−ＣＨ₂−（但し、Ｉｎｄｏ：インドール環）］であり、Ｍが銅であるビス−Ｌ-トリプトファン銅錯化合物（化合物Ｎｏ．１２）、
Ｒ¹、Ｒ²が共にトレオニン側鎖[ＣＨ₃ＣＨ（ＯＨ）-］であり、Ｍが銅であるビス−Ｌ-トレオニン銅錯化合物（化合物Ｎｏ．１４）、
Ｒ¹、Ｒ²が共にバリン側鎖[（ＣＨ₃）₂ＣＨ−］であり、Ｍが銅であるビス−Ｌ-バリン銅錯化合物（化合物Ｎｏ．１５）、
Ｒ¹、Ｒ²が共にヒドロキシプロリン側鎖[−ＣＨ₂ＣＨ（ＯＨ）ＣＨ₂−］であり、Ｍが銅であるビス−Ｌ-ヒドロキシプロリン銅錯化合物（化合物Ｎｏ．１７）、
Ｒ¹、Ｒ²が共にプロリン側鎖[−（ＣＨ₂）₃−］であり、Ｍが銅であるビス−Ｌ-プロリン銅錯化合物（化合物Ｎｏ．１９）、
Ｒ¹、Ｒ²が共にフェニルアラニン側鎖[Ｐｈ-ＣＨ₂−（但し、Ｐｈ：フェニル基）］であり、Ｍが銅であるビス−Ｌ-フェニルアラニン銅錯化合物（化合物Ｎｏ．２０）、
Ｒ¹、Ｒ²が共にリジン側鎖[Ｈ₂Ｎ（ＣＨ₂）₄−］であり、Ｍが銅であるビス−Ｌ-リジン銅錯化合物（化合物Ｎｏ．２１）、
Ｒ¹、Ｒ²が共にロイシン側鎖[（ＣＨ₃）₂ＣＨＣＨ₂−］であり、Ｍが銅であるビス−Ｌ-ロイシン銅錯化合物（化合物Ｎｏ．３０）等が挙げられる。
【００２８】
また、このようなアミノ酸金属錯化合物[I]の塩（アミノ酸塩の金属錯化合物）としては、塩基性アミノ酸金属錯化合物の場合は、無機酸塩、有機酸塩、脂肪酸塩およびアニオン性界面活性剤塩が用いられる。
上記無機酸としては、塩酸、臭化水素酸、沃化水素酸、硫酸、硝酸、リン酸、炭酸等が挙げられる。有機酸としては、酢酸、安息香酸、ソルビン酸、グリコール酸、乳酸、酒石酸、蓚酸等が挙げられる。脂肪酸としては、カプリル酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、ヤシ油脂肪酸、牛脂脂肪酸等が挙げられる。アニオン界面活性剤としては、ラウリル硫酸エステル、ラウリルエーテル硫酸エステル、ドデシルベンゼンスルホン酸等が挙げられる。
【００２９】
また酸性アミノ酸金属錯化合物の場合は、上記酸性アミノ酸のナトリウム塩、カリウム塩、カルシウム塩などが挙げられる。
その他、金属錯化合物のアミノ酸側鎖の一方が、塩基性アミノ酸側鎖であり、他方が酸性アミノ酸側鎖からなる、塩基性アミノ酸と酸性アミノ酸との塩の金属錯化合物等が挙げられる。
【００３０】
このようなアミノ酸金属錯化合物[I]の塩としては、具体的には、例えば、上記式[I]中、Ｒ¹、Ｒ²が共にアルギニン側鎖[Ｈ₂ＮＣ（＝ＮＨ）ＮＨ（ＣＨ₂）₃−]であり、Ｍが銅であるビス−Ｌ-アルギニン銅錯化合物の塩酸塩（ビス−Ｌ−アルギニン・１塩酸塩銅錯化合物：化合物Ｎｏ．４）、
Ｒ¹、Ｒ²が共にオルニチン側鎖[Ｈ₂Ｎ（ＣＨ₂）₃−]であり、Ｍが銅であるビス−Ｌ-オルニチン銅錯化合物の塩酸塩（ビス−Ｌ−オルニチン・１塩酸塩銅錯化合物：化合物Ｎｏ．６）、
Ｒ¹、Ｒ²が共にＬ−２，４−ジアミノブチル酸側鎖[Ｈ₂Ｎ−（ＣＨ₂）₂−]であり、Ｍが銅であるビス−Ｌ-２，４−ジアミノブチル酸（DABA）銅錯化合物の塩酸塩（ビス−Ｌ−２，４−ジアミノブチル酸（DABA）・１塩酸塩銅錯化合物：化合物Ｎｏ．９）、
Ｒ¹、Ｒ²が共にＤＬ−２，３−ジアミノプロピオン酸(DAPA)側鎖[Ｈ₂Ｎ−ＣＨ₂−]であり、Ｍが銅であるビス−ＤＬ-２，３−ジアミノプロピオン酸(DAPA)銅錯化合物の塩酸塩（ビス−ＤＬ−２，３−ジアミノプロピオン酸（DAPA）・１塩酸塩銅錯化合物：化合物Ｎｏ．１０）、
Ｒ¹、Ｒ²が共にＬ−４−チアリジン側鎖[Ｈ₂Ｎ（ＣＨ₂）₂ＳＣＨ₂−]であり、Ｍが銅であるビス−Ｌ-４−チアリジン銅錯化合物の塩酸塩（ビス−Ｌ−４−チアリジン・１塩酸塩銅錯体：化合物Ｎｏ．１３）、
Ｒ¹、Ｒ²が共にヒスチジン側鎖[Ｉｍｉ−ＣＨ₂−（但し、Ｉｍｉ：イミダゾール環）]であり、Ｍが銅であるビス−Ｌ-ヒスチジン銅錯化合物の塩酸塩（ビス−Ｌ−ヒスチジン・１塩酸塩銅錯体：化合物Ｎｏ．１６）、
Ｒ¹、Ｒ²が共にヒドロキシリジン側鎖[Ｈ₂ＮＣＨ₂ＣＨ（ＯＨ）（ＣＨ₂）₂−]であり、Ｍが銅であるビス−ＤＬ-ヒドロキシリジン銅錯化合物の塩酸塩（ビス−ＤＬ−ヒドロキシリジン・１塩酸塩銅錯体：化合物Ｎｏ．１８）、
Ｒ¹、Ｒ²が共にリジン側鎖[Ｈ₂Ｎ（ＣＨ₂）₄−]であり、Ｍが銅であるビス−Ｌ-リジン銅錯化合物の塩酸塩（ビス−Ｌ−リジン・１塩酸塩銅錯化合物：化合物Ｎｏ．２２）、
Ｒ¹、Ｒ²が共にリジン側鎖[Ｈ₂Ｎ（ＣＨ₂）₄−]であり、Ｍが銅であるビス−Ｌ-リジン銅錯化合物の炭酸水素塩（ビス−Ｌ−リジン・１炭酸水素塩銅錯化合物：化合物Ｎｏ．２３）、
Ｒ¹、Ｒ²が共にリジン側鎖[Ｈ₂Ｎ（ＣＨ₂）₄−]であり、Ｍが銅であるビス−Ｌ-リジン銅錯化合物のドデシルベンゼンスルホン酸（DBSA）塩（ビス−Ｌ−リジン・ＤＢＳＡ塩銅錯化合物：化合物Ｎｏ．２４）、
Ｒ¹、Ｒ²が共にリジン側鎖[Ｈ₂Ｎ（ＣＨ₂）₄−]であり、Ｍが銅であるビス−Ｌ-リジン銅錯化合物のラウリン酸（LauA）塩（ビス−Ｌ−リジン・ＬａｕＡ塩銅錯化合物：化合物Ｎｏ．２５）、
Ｒ¹、Ｒ²が共にリジン側鎖[Ｈ₂Ｎ（ＣＨ₂）₄−]であり、Ｍが銅であるビス−Ｄ-リジン銅錯化合物の塩酸塩（ビス−Ｄ−リジン・１塩酸塩銅錯化合物：化合物Ｎｏ．２６）、
Ｒ¹、Ｒ²が共にリジン側鎖[Ｈ₂Ｎ（ＣＨ₂）₄−]であり、Ｍが銅であるビス−ＤＬ-リジン銅錯化合物の塩酸塩（ビス−ＤＬ−リジン・１塩酸塩銅錯化合物：化合物Ｎｏ．２７）、
Ｒ¹、Ｒ²が共にリジン側鎖[Ｈ₂Ｎ（ＣＨ₂）₄−]であり、Ｍが亜鉛であるビス −Ｌ-リジン亜鉛錯化合物の塩酸塩（ビス−Ｌ−リジン・１塩酸塩亜鉛錯化合物：化合物Ｎｏ．３１）、
Ｒ¹、Ｒ²が共にリジン側鎖[Ｈ₂Ｎ（ＣＨ₂）₄−]であり、Ｍがマグネシウムであるビス−Ｌ-リジンマグネシウム錯化合物の塩酸塩（ビス−Ｌ−リジン・１塩酸塩マグネシウム錯化合物：化合物Ｎｏ．３２）等が挙げられる。
【００３１】
また上記式[I]中、Ｒ¹、Ｒ²が互いに異なるものとしては、上記式[I]中、Ｒ¹がリジン側鎖[Ｈ₃Ｎ⁺（ＣＨ₂）₄−]であり、Ｒ²がアスパラギン酸側鎖［^-ＯＯＣＣＨ₂−]であり、Ｍが銅であるＬ−リジン・Ｌ-アスパラギン酸塩の銅錯化合物（Ｌ−リジン・Ｌ-アスパラギン酸塩銅錯化合物：化合物Ｎｏ．２８）、
また上記式[I]中、Ｒ¹がリジン側鎖[Ｈ₃Ｎ⁺（ＣＨ₂）₄−]であり、Ｒ²がグルタミン酸側鎖［^-ＯＯＣ−（ＣＨ₂）₂−]であり、Ｍが銅であるＬ−リジン・Ｌ-グルタミン酸塩の銅錯化合物（Ｌ−リジン・Ｌ-グルタミン酸塩銅錯化合物：化合物Ｎｏ．２９）等が挙げられる。
【００３２】
このようなアミノ酸金属錯化合物類は、本発明の農園芸用種子消毒剤中に１種または２種以上含まれていてもよい。
上記例示のアミノ酸金属錯化合物[I]を表１にまとめて示す。
このようなアミノ酸金属錯化合物類のうちでは、下記表１中付番１、４〜７、９〜１１、１３〜１４、１６〜１９、２１〜２７が好ましく、さらには付番４、６〜７、９〜１１、１３、１７〜１８、２１〜２７が水溶性に優れ、特に種子消毒効果に優れるため好ましい。
【００３３】
【表１】

【００３４】
この化合物番号は、後述する実施例、試験例でも参照される。
上記式[I]中、Ｒ¹とＲ²とが異なる錯化合物では、Ｒ¹が塩基性アミノ酸側鎖であり、Ｒ²が酸性アミノ酸側鎖である場合のように塩が形成されている場合に安定的に単一な錯化合物が得られる。
本発明においては、上記式[I]中、Ｒ¹が塩基性アミノ酸側鎖であり、Ｒ²が酸性アミノ酸側鎖であるアミノ酸金属錯化合物（塩基性アミノ酸の酸性アミノ酸塩の金属錯化合物）は、下記式[II]で表される。
【００３５】
【化４】

【００３６】
[式[II]中、Ｒ³は、塩基性アミノ酸の側鎖を示し 、Ｒ⁴は酸性アミノ酸の側鎖を示し、Ｍは、銅、亜鉛、マンガン、鉄およびマグネシウムのうちの何れかを示す。]
このような金属錯化合物[II]としては、上記例示のアミノ酸金属錯化合物[I]のうちでは、Ｌ−リジン・Ｌ-アスパラギン酸塩銅錯化合物（化合物Ｎｏ．２８）および、Ｌ−リジン・Ｌ-グルタミン酸塩銅錯化合物（化合物Ｎｏ．２９）が、前記式[II]で表される化合物すなわち塩基性アミノ酸の酸性アミノ酸塩の金属錯化合物に含まれる。
【００３７】
すなわち、Ｌ−リジン・Ｌ-アスパラギン酸塩銅錯化合物（化合物Ｎｏ．２８）は、式[II]中、塩基性アミノ酸側鎖Ｒ³がリジン側鎖[Ｈ₃Ｎ⁺（ＣＨ₂）₄−]であり、酸性アミノ酸側鎖Ｒ⁴がアスパラギン酸側鎖［^-ＯＯＣＣＨ₂−]であり、Ｍが銅である錯化合物に相当している。
またＬ−リジン・Ｌ-グルタミン酸塩銅錯化合物（化合物Ｎｏ．２９）は、上記式[II]中、塩基性アミノ酸側鎖Ｒ³がリジン側鎖[Ｈ₃Ｎ⁺（ＣＨ₂）₄−]であり、酸性アミノ酸側鎖Ｒ⁴がグルタミン酸側鎖［^-ＯＯＣ（ＣＨ₂）₂−]であり、Ｍが銅である錯化合物に相当している。
＜アミノ酸金属錯化合物類の製造＞
上記式[I]または[II]で表されるアミノ酸金属錯化合物あるいはその塩（アミノ酸金属錯化合物類）は、前記の文献等に記載の従来より公知の方法にて製造できる。
【００３８】
例えば、式[I]中、Ｍが銅であるアミノ酸銅錯化合物[I-a]は、下記反応式で示すように、各種アミノ酸(a)の水溶液中に塩基性炭酸銅をアミノ酸に対して銅として１／２当量になるように加えて、必要に応じて加熱して反応させることにより好適に製造できる。なお、上記塩基性炭酸銅に代えて、亜酸化銅、硫酸銅、塩化銅、水酸化銅、塩基性塩化銅あるいは塩基性硫酸銅を用いてもよい。
【００３９】
【化５】

【００４０】
[式(a)中、Ｒ¹は、上記と同様、アミノ酸側鎖を示す。]
また、前記式[II]中、Ｍが銅であるアミノ酸銅錯化合物[II-a]は、下記式に示すように、遊離の塩基性アミノ酸(a-2)および酸性アミノ酸(a-3)をそれぞれ等モルずつ水に溶解して塩基性アミノ酸の酸性アミノ酸塩溶液を調製し、この水溶液に塩基性炭酸銅をアミノ酸に対して銅として１／２当量になるよう加えて、必要に応じて加熱し、反応させることにより塩基性アミノ酸の酸性アミノ酸塩の銅錯化合物[II-a]を好適に製造できる。
【００４１】
【化６】

【００４２】
[但し、上記反応式中、Ｒ³は、塩基性アミノ酸側鎖を示し、Ｒ⁴は、酸性アミノ酸側鎖を示す。]
上記式[II]中、Ｍが銅以外の他の金属のアミノ酸錯化合物も上記と同様に製造できる。上記アミノ酸(a-2)、(a-3)および上記塩基性炭酸銅（ＣｕＣＯ₃・Ｃｕ（ＯＨ）₂ ・Ｈ₂Ｏ）等の金属化合物は何れも公知物質であり、市販品を使用すればよい。
【００４３】
上記反応の際に使用されるアミノ酸としては、中性アミノ酸、塩基性アミノ酸、酸性アミノ酸等が挙げられる。中性アミノ酸としては、具体的には、例えば、アスパラギン、アラニン、イソロイシン、グリシン、グルタミン、セリン、チロシン、トリプトファン、トレオニン、バリン、ヒドロキシプロリン、フェニルアラニン、プロリン、メチオニン、ロイシン等が挙げられ、
これらのうちで、得られる化合物の種子消毒効果の点を考慮すると、アラニン、イソロイシン、グリシン、セリン、チロシン、トレオニン、バリン、ヒドロキシプロリン、プロリン、メチオニンが好ましく用いられる。
【００４４】
塩基性アミノ酸としては、例えば、アルギニン、ヒスチジン、リジン、ヒドロキシリジン、オルニチン、２，４−ジアミノブチル酸、２，３−ジアミノプロピオン酸、４−チアリジン等が挙げられ、
これらのうちで、得られる化合物の種子消毒効果の点を考慮すると、２，４−ジアミノブチル酸、アルギニン、リジン、ヒドロキシリジン、オルニチン、２，３−ジアミノプロピオン酸、４−チアジリンが好ましく用いられる。
【００４５】
酸性アミノ酸としては、例えば、アスパラギン酸、グルタミン酸等が挙げられる。
なお、上記塩基性アミノ酸としては、その遊離物あるいは無機酸塩、有機酸塩、脂肪酸塩およびアニオン界面活性剤塩を用いることもできる。上記無機酸としては、塩酸、臭化水素酸、沃化水素酸、硫酸、硝酸、リン酸、炭酸等が挙げられる。有機酸としては、酢酸、安息香酸、ソルビン酸、グリコール酸、乳酸、酒石酸、蓚酸等が挙げられる。脂肪酸としては、カプリル酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、ヤシ油脂肪酸、牛脂脂肪酸等が挙げられる。アニオン界面活性剤としては、ラウリル硫酸エステル、ラウリルエーテル硫酸エステル、ドデシルベンゼンスルホン酸等が挙げられる。
【００４６】
また、上記酸性アミノ酸としては、その遊離物あるいは金属塩を用いることもできる。この金属としてはナトリウム、カリウムおよびカルシウムが挙げられる。
また、上記アミノ酸金属錯化合物類を製造する際に用いられるアミノ酸としては、光学活性体のＬ体あるいはＤ体であってもよく、光学的に不活性なラセミ体であってもよい。なお、これらの中でリジンやオルニチンなどの塩基性アミノ酸が殺菌効果を増強する上で特に好適である。上記のようなアミノ酸金属錯化合物類を製造する際には、金属Ｍの単体、該金属の亜酸化物、該金属の水酸化物の他、これら金属の硫酸塩、塩酸塩、硝酸塩、炭酸塩、酢酸塩、シュウ酸塩等を用いることができる。金属Ｍとしては、銅、亜鉛、マンガン、鉄およびマグネシウムが挙げられる。本発明で用いられるアミノ酸金属錯化合物では、上記式[I]から明らかなように、アミノ酸と金属の結合モル比は２：１であることが好ましい。
【００４７】
また、アミノ酸金属錯化合物の塩（アミノ酸塩の金属錯体）は、例えば、
Ｌ−リジン・１塩酸塩等のアミノ酸塩と、金属供給源の亜酸化銅、塩基性炭酸銅などとを必要により加熱し、反応させることにより得られる。
＜農園芸用種子消毒剤＞
本発明に係る農園芸用種子消毒剤は、上記アミノ酸金属錯化合物類を有効成分として含有しているが、このアミノ酸金属錯化合物類の含有率は、この消毒剤の剤型、その使用方法などの条件により適宜変更でき、特に制限されないが、通常、０.１〜９５重量％程度である。
【００４８】
また、本発明に係る農園芸用種子消毒剤には、上記アミノ酸金属錯化合物類は、１種または２種以上含まれていてもよい。
また、本発明に係る農園芸用種子消毒剤は、上記アミノ酸金属錯化合物類のほかに、他の公知の活性化合物、例えば、殺菌剤、殺虫剤、殺ダニ剤、殺線虫剤、昆虫生育調節剤、除草剤、鳥類忌避剤、植物成長調節剤、肥料、土壌改良剤などを含んでいてもよい。このようにアミノ酸金属錯化合物類と他の活性化合物とを含有する農園芸用種子消毒剤では、適用範囲（適用病害、使用方法、使用時期など）の拡大を図ることができ、場合によっては配合した種々の有効成分の相乗効果も期待できる。
【００４９】
本発明においては、アミノ酸[上記式(a)、(a-2)、(a-3)で表されるようなアミノ酸金属錯化合物類形成性のアミノ酸]と、金属（上記アミノ酸金属錯化合物中に含まれるものと同様の金属）あるいは無機金属化合物とを、好ましくは化学量論量すなわち２：１のモル比で製剤中に配合し、使用時にこの製剤を水で希釈することにより、上記アミノ酸金属錯化合物類を生成する農園芸用種子消毒剤とすることもできる。
【００５０】
この際用いられる上記金属化合物として、例えば、金属亜酸化物；金属水酸化物；硫酸塩、塩酸塩、硝酸塩、炭酸塩、酢酸塩、蓚酸塩等の金属塩等を用いることができる。
金属としては、銅、亜鉛、マンガン、鉄、マグネシウム等が挙げられ、中でも銅が好ましい。銅系の無機化合物（無機銅化合物）としては、亜酸化銅、硫酸銅、塩化銅、水酸化銅、塩基性塩化銅、塩基性硫酸銅等が挙げられる。
【００５１】
また、銅あるいは上記無機銅化合物を有効成分とする既存の農薬製剤と、前記アミノ酸とを混合することにより種子消毒活性の増強効果が期待できる。
本発明に係る農園芸用種子消毒剤は、上記アミノ酸金属錯化合物類を有効成分として含有する限り、その剤型は特に制限されず、その使用目的等に応じて従来公知の処方により種々の剤型のものを調製し得る。
【００５２】
例えば、アミノ酸金属錯化合物類と後述するような各種担体と界面活性剤とその他の製剤用補助剤等とを配合して、例えば、常法によって、水和剤、顆粒水和剤、乳剤、液剤、フロアブル剤、微粒剤、粒剤、種子用コーティング剤などの各種剤型に製剤化して用いることができる。
上記のように各種剤型の農園芸用種子消毒剤を製造する際に用いられる担体には、固体担体、液体担体などがあり、このうちで固体担体としては、例えば、カオリン、ベントナイト、クレー、モンモリロナイト、タルク、バーミキュライト、アタパルガイド、珪藻土、珪砂、合成ケイ酸塩、炭酸カルシウム、燐酸カルシウム、アルミナ、ホワイトカーボン、硫安、尿素、デンプン、結晶セルロース、大豆粉、クルミ穀粉、タバコ茎粉等が挙げられる。
【００５３】
液体担体としては、例えば、水、アルコール類（例：メタノール、エタノール、イソプロピルアルコール、エチレングリコール、グリセリン等）、エーテル類（例：ジオキサン、テトラヒドロフラン等）、ケトン類（例：アセトン、メチルエチルケトン等）、エステル類（例：脂肪酸のグリセリンエステル等）、スルホキシド類（例：ジメチルスルホキシド等）、脂肪族または脂環式炭化水素類（例：シクロヘキサン、パラフィン類等）などが挙げられる。
【００５４】
また、上記界面活性剤としては、例えば、アルキル硫酸エステル塩、アルキル（アリール）スルホン酸塩、ジアルキルスルホコハク酸塩、ポリオキシエチレンアルキルアリールエーテルリン酸塩などの陰イオン界面活性剤；
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アルキルアリールエーテル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン酸エステルなどの非イオン性界面活性剤；
などが挙げられる。
【００５５】
また、製剤用補助剤としては、物理性改良剤、分解防止剤あるいは粘結剤としてのカルボキシメチルセルロース（ＣＭＣ）、ポリビニルアルコール（ＰＶＡ）、アラビアゴム、ゼラチン、カゼイン、アルギン酸ソーダ、トラガカントゴム、キサンタンガムなどが挙げられる。
＜農園芸用種子消毒剤の使用方法＞
本発明に係る農園芸用種子消毒剤は、その剤型、用途（例：種子消毒用、育苗箱施用用）、適用病害、使用時期などに応じて常法に従って用いられる。
【００５６】
また、本発明では、予めアミノ酸と金属化合物あるいはその塩を配合してなる配合物を調製しておき、使用時にこの配合物を水で希釈することによりアミノ酸金属錯化合物を形成させて、本発明に係る農園芸用種子消毒剤として使用してもよい。また、本発明においては、上記金属あるいは該金属の水酸化物等の金属化合物、例えば水酸化銅、塩基性塩化銅、塩基性硫酸銅などを有効成分とする既存の農薬製剤に、リジンなどのアミノ酸を添加し水で希釈することによりアミノ酸金属錯化合物を形成させて、農園芸用種子消毒剤として使用することもできる。この際、アミノ酸は、金属１モルに対して、化学量論的には２モルで用いればよいが、通常、０．１〜２．５モルの量で用いられる。
【００５７】
また、アミノ酸を添加する時期は、上記金属あるいは該金属の水酸化物等の金属化合物、例えば水酸化銅、塩基性塩化銅、塩基性硫酸銅などを有効成分とする既存の農薬製剤の薬液調製時期に限定されるものでなく、例えば、既存の農園芸用殺菌剤調製後、浸種前であってもよく、浸種期間中であってもよく、浸種期間終了前であれば、何れの時期においても添加することができ、また一度に添加してもよく、複数回に分けて少量ずつ添加してもよい。また、種子消毒処理した種籾をアミノ酸を含有する液に浸種してもよい。
【００５８】
本発明に係る農園芸用種子消毒剤の使用方法についてさらに詳説すると、この消毒剤の用途は特に限定されるものではなく、また種子消毒用、育苗箱施用用などの何れの用途にも使用することができる。またこの農園芸用種子消毒剤の使用量は、有効成分として含まれるアミノ酸金属錯化合物その他の薬効成分の種類、適用対象（例えば、対象作物、対象病害、その発生状況等）、使用時期などに応じて適宜変えることができる。
【００５９】
例えば、本発明の農園芸用種子消毒剤をイネの種子消毒剤として使用するには、一般的な種子消毒剤の使用方法に準ずればよい。より具体的には、水和剤、乳剤、フロアブル剤、顆粒水和剤などの液状で使用する農園芸用種子消毒剤では、該消毒剤を水などで希釈して有効成分濃度を５０〜５００００ｐｐｍ、好ましくは２００〜２００００ｐｐｍとして、この薬液中にイネ種籾を１０〜６０分間浸漬（短時間浸漬）、または２４時間〜４８時間浸漬（長時間浸漬）すればよい。
【００６０】
また、水和剤、フロアブル剤、顆粒水和剤などの液状で使用する製剤（但し、乳剤を除く。）を、必要に応じて水などで希釈して、種子重量の１〜５重量％の量（活性成分量として、０．５〜２０ｇ／種子重量１ｋｇ）で種子に吹き付け処理してもよく、またこのような量となるようにモルタルミキサーなどを用いて均一に種子に塗抹処理してもよい。
【００６１】
その他、水和剤などの固体製剤を種子重量の０．１〜２重量％の量（活性成分量として０．５〜２０ｇ／種子重量１ｋｇ）で種子の表面に粉衣処理するなどの方法で用いてもよい。
本発明に係る農園芸用種子消毒剤を育苗箱（サイズ：縦×横×高さ＝６０ｃｍ×３０ｃｍ×３ｃｍ）に散布する場合、その水和剤、乳剤、フロアブル剤を水に希釈して、有効成分濃度が１００〜１００００ｐｐｍ、好ましくは４００〜４００００ｐｐｍとし、この薬液をイネ種籾播種後の育苗箱の上方から散布機にて２０〜２００ｍｌ／育苗箱の量で噴霧するか、あるいはジョウロなどを用いて２００〜１０００ｍｌ／育苗箱の量で灌注するなどの方法を採用できる。
【００６２】
また、本発明に係る農園芸用種子消毒剤が、粉剤、粒剤などである場合、これをそのままイネ種籾の播種後覆土前あるいは覆土後に育苗箱の上方から直接手にて、あるいは散布機にて５〜５０ｇ／育苗箱の量（活性成分として、０．１〜１０ｇ／育苗箱）で散布するなどの方法を採用してもよい。
【００６３】
【発明の効果】
本発明に係る農園芸用種子消毒剤は、イネ種子をはじめとする各種種子に対して優れた消毒活性を有しているが、この種子消毒剤をイネ種子消毒剤、イネ育苗箱施用消毒剤として用いれば、特に、イネ苗立枯細菌病、イネ籾枯細菌病、イネ褐条病に対して安定した高い種子消毒効果を発揮し、これらの病害を有効に防除することができる。
【００６４】
また、本発明に係る農園芸用種子消毒剤中に含まれる有効成分のアミノ酸金属錯化合物類は、極めて低毒性（経口：＞１０００ｍｇ／ｋｇ）である。本発明の農園芸用種子消毒剤は、有効成分がアミノ酸金属錯化合物等であるため、この錯化合物を合成する際に用いられる金属、例えば、銅の使用量を従来の薬剤の半量以下に抑えることができ、また他方の成分であるアミノ酸は生分解性もよく、環境汚染がほとんどない。
【００６５】
【実施例】
次に、本発明の農園芸用種子消毒剤およびその使用例、該農園芸用種子消毒剤に含まれるアミノ酸金属錯化合物の製造例についてさらに具体的に説明するが、本発明はかかる実施例により何ら制限されるものではない。
なお、実施例、製造例中、（部）とあるのはすべて重量部であり、また％は重量％である。
【００６６】
【製造例１】
（ビス−Ｌ−セリン銅錯化合物、化合物Ｎｏ．１１）
Ｌ−セリン５．０００ｇ（４７．５８ｍｍｏｌ）を蒸留水１０ｍｌに溶かし、これに塩基性炭酸銅５．６７８ｇ（２３．７９ｍｍｏｌ）を突沸させないように徐々に加えた。得られた混合物を６０℃で３０分間加熱撹拌した後、ろ過した。濾紙上に残存する不溶物を熱水５ｍｌで洗い、この洗液とろ液とを一緒にした。一緒にしたろ液を半固体状態まで減圧濃縮し、メタノールを１０ｍｌ加え６０℃で加熱溶解させた。これを室温で放置すると直ちに結晶が析出した。この結晶をろ取し、減圧乾燥することにより、Ｌ−セリンの銅錯化合物を６．４０２ｇ（収率８７．４５％）得た。
【００６７】
IR（KBr拡散反射法）：3344,3255,3213,3132,2937,1664,1631,1606,1394,1328,1276,1164,1099,1058,985,707cm^-1
【００６８】
【製造例２】
（ビス−Ｌ−リジン・１塩酸塩銅錯化合物、化合物Ｎｏ．２２）
Ｌ−リジン・１塩酸塩、５．０００ｇ（２７．３７ｍｍｏｌ）を蒸留水１０ｍｌに溶かし、これに亜酸化銅０．９７９ｇ（６．８４ｍｍｏｌ）を加えた。得られた混合物を６０℃で１２時間加熱撹拌した後、ろ過した。不溶物を熱水５ｍｌで洗い、この洗液とろ液を一緒にした。一緒にしたろ液を半固体状態まで減圧濃縮し、メタノールを１０ｍｌ加え６０℃で加熱溶解させた。これを室温で放置すると直ちに結晶が析出した。この結晶をろ取し、減圧乾燥することにより、Ｌ−リジン・１塩酸塩の銅錯化合物を６．０１８ｇ（収率９５．０４％）得た。
【００６９】
IR（KBr拡散反射法）：3444,3259,3010,2941,1660,1584,1523,1392,1134cm^-1
【００７０】
【製造例３】
（ビス−Ｌ−リジン・１炭酸水素塩銅錯化合物、化合物Ｎｏ．２３）
Ｌ−リジン（遊離塩基）５．０００ｇ（３４．２０ｍｍｏｌ）を蒸留水１０ｍｌに溶かし、これに塩基性炭酸銅４．０８２ｇ（１７．１０ｍｍｏｌ）を突沸させないように徐々に加えた。得られた混合物を６０℃で３０分間加熱撹拌した後、室温で撹拌下に炭酸ガスを２時間通気しｐＨを７．０に調整した。ろ過後、不溶物を熱水５ｍｌで洗い、この洗液とろ液を一緒にした。一緒にしたろ液を半固体状態になるまで減圧濃縮し、メタノールを１０ｍｌ加え６０℃で加熱溶解させた。これを室温で放置すると直ちに結晶が析出した。この結晶をろ取し、減圧乾燥することにより、Ｌ−リジン炭酸水素塩の銅錯化合物を４．９８８ｇ（収率７８．９３％）得た。
【００７１】
IR（KBr拡散反射法）：3220,2968,2869,1643,1458,1359,1240,1199,1083,918,877,767,700cm^-1
【００７２】
【製造例４】
（ビス−Ｌ−オルニチン・１塩酸塩銅錯化合物、化合物Ｎｏ．６）
Ｌ−オルニチン（遊離塩基）５.０００ｇ（３７．８３ｍｍｏｌ）を蒸留水１０ｍｌに溶かし、これに塩化銅２．５４３ｇ（１８．９２ｍｍｏｌ）を加えた。得られた混合物を６０℃で３０分間加熱撹拌した後、半固体状態になるまで減圧濃縮した。これに熱メタノールを１０ｍｌ加え６０℃で加熱溶解させた。これを室温で放置すると直ちに結晶が析出した。この結晶をろ取し、減圧乾燥することにより、Ｌ−オルニチン・１塩酸塩の銅錯化合物を８．１８４ｇ（収率９６．４％）得た。
【００７３】
IR（KBr拡散反射法）：3396,3232,3012,1625,1593,1523,1400,1344,1134,1053,813,648cm^-1
【００７４】
【製造例５】
（Ｌ−リジン・Ｌ−グルタミン酸塩銅錯化合物、化合物Ｎｏ．２９）
Ｌ−リジン（遊離塩基）２．０００ｇ（１３．６８ｍｍｏｌ）およびＬ−グルタミン酸２．０１３ｇ（１３．６８ｍｍｏｌ）を蒸留水１０ｍｌに溶かし、これに塩基性炭酸銅３．２６６ｇ（１３．６８ｍｍｏｌ）を突沸させないように徐々に加えた。得られた混合物を６０℃で３０分間加熱撹拌した後、ろ過した。不溶物を熱水５ｍｌで洗い、この洗液とろ液を一緒にした。一緒にしたろ液を半固体状態になるまで減圧濃縮し、メタノールを１０ｍｌ加え６０℃で加熱溶解させた。次いで冷蔵庫で一夜放置すると結晶が析出した。この結晶をろ取し、減圧乾燥することにより、Ｌ−リジン・Ｌ−グルタミン酸塩の銅錯化合物を４．５２４ｇ（収率８４．６２％）得た。
【００７５】
IR（KBr拡散反射法）：3280,3242,3028,2945,2862,1618,1556,1504,1398,1334,1145,1058,798,659cm^-1
【００７６】
【実施例１】
（水和剤）
ビス−Ｌ−リジン・１塩酸塩銅錯化合物（化合物Ｎｏ．２２）３０部、アルキルベンゼンスルホン酸ナトリウム３部、ポリオキシエチレンノニルフェニルエーテル５部およびクレー６２部を均一に混合・粉砕して、有効成分を３０％含有する水和剤を得た。
【００７７】
【実施例２】
（乳剤）
ビスグリシン銅錯化合物（化合物Ｎｏ．７）３０部、メチルエチルケトン５５部およびポリオキシエチレンノニルフェニルエーテル１５部を混合・溶解して、有効成分を３０％含有する乳剤を得た。
【００７８】
【実施例３】
（粒剤）
ビス−Ｌ−オルニチン・１塩酸塩銅錯化合物（化合物Ｎｏ．６）５部、ラウリルサルフェート１．５部、リグニンスルホン酸カルシウム１．５部、ベントナイト２５部およびクレー６７部を均一に混合し、これに水１５部を加えて混練機で混練した後、造粒機で造粒し、流動乾燥機で乾燥して、有効成分を５％含有する粒剤を得た。
【００７９】
【実施例４】
（フロアブル剤）
ビス−Ｌ−アラニン銅錯化合物（化合物Ｎｏ．２）４０部、ラウリルサルフェート２部、アルキルナフタレンスルホン酸ソーダ２部、ヒドロキシプロピルセルロース１部および水５５部を均一に混合し、有効成分を４０％含有するフロアブル剤を得た。
【００８０】
【実施例５】
（水和剤）
Ｌ−アルギニン・１塩酸塩２３．４部、塩基性炭酸銅６．６部、アルキルベンゼンスルホン酸ナトリウム３部、ポリオキシエチレンノニルフェニルエーテル５５部およびクレー６２部を均一に混合・粉砕して、水和剤を得た。本水和剤は使用時に水で希釈すると、有効成分であるビス−Ｌ−アルギニン・１塩酸塩銅錯化合物（化合物Ｎｏ．４）を２８．８％含有相当分を生成する。
【００８１】
次に、本発明に係る農園芸用種子消毒剤の各種植物病害に対する防除活性の試験例を示すが、本発明は、以下の試験例に限定されるものではない。
【００８２】
【試験例１】
（イネ苗立枯細菌病防除のための種子消毒効果試験）
供試籾としては、イネ（品種：きらら３９７）の開花期にイネ苗立枯細菌病菌（Pseudomonas plantarii）の濃厚菌懸濁液（１０⁴／ｍｌ）を噴霧接種して得たイネ苗立枯細菌病感染籾を用いた。
【００８３】
種子消毒液（薬液）は実施例２に準じて調製した、第２表に示す種々のアミノ酸金属錯化合物の水和剤または対照剤を、水で所定濃度に希釈して調製した。
この薬液中に、上記方法で得られたイネ苗立枯細菌病菌感染籾を、種籾と薬液との容量比（ｖ／ｖ）が１対１の割合になるようにして加え、２０℃で２４時間にわたり該種籾を浸漬させ、消毒した。消毒後の種籾を、２０℃で３日間水に浸漬した後、水を切り３０℃で２４時間催芽させた。そして、鳩胸状になった種籾を慣用の箱育苗法に準じてクミアイ粒状培土Ｋ（呉羽化学工業株式会社製）に播種し、３２℃で２日間出芽させた。その後はガラス温室内で栽培管理した。
【００８４】
発病の有無の調査は、播種２１日後（２．５葉期）に下記の調査基準によりイネ苗立枯細菌病発病苗数と健全苗数を調査し（１箱当たり約１５０本）、下記の式（１）により発病度を求めた。
発病の調査基準
Ｎ₀： 発病してない苗数
Ｎ₁： 葉身に発病による白化あるいは黄化が認められる苗数
Ｎ₂： 葉身が発病により白化し、生育が劣る苗数
Ｎ₃： 枯死
【００８５】
【数１】

【００８６】
本試験は、１区３連制で行い、その平均発病度を算出し、次式より防除価（％）を求めた。この防除価を下記基準により防除効果の評価値に換算した。
その結果を表２に示す。
【００８７】
【数２】

【００８８】
防除効果の評価値 防 除 価
５ ９５％以上
４ ９０〜９５％未満
３ ７０〜９０％未満
２ ４０〜７０％未満
１ ４０％未満
またイネに対する薬害については出芽状態および生育程度などについて観察し、下記の薬害調査指標の基準で表示した。
【００８９】
その試験結果を表２に要約して示す。
薬害の調査指標
５：激甚、 ４：甚、 ３：多、 ２：若干、 １：わずか、 ０：なし
【００９０】
【表２】

【００９１】
【試験例２】
（イネ籾枯細菌病防除のための種子消毒効果試験）
供試籾としては、イネ（品種：きらら３９７）籾にイネ籾枯細菌病菌（Pseudomonas glumae）の濃厚菌懸濁液（１０⁸／ｍｌ）を減圧接種して得たイネ籾枯細菌病菌感染籾を用いた。種子消毒液は実施例２に準じて調製した、表３に示す種々のアミノ酸金属錯化合物の水和剤または対照剤を、水で所定濃度に希釈して調製した。
【００９２】
この薬液中に、上記方法で得られたイネ籾枯細菌病菌感染籾を、種籾と薬液との容量比（ｖ／ｖ）が１対１の割合になるようにして加え、２０℃で２４時間にわたり該種籾を浸漬して、消毒した。消毒後の種籾は、２０℃で３日間水に浸種した後、水を切り３０℃で２４時間催芽させた。そして、鳩胸状になった種籾を慣用の箱育苗法に準じてクミアイ粒状培土Ｋ（呉羽化学工業株式会社製）に播種し、３２℃で２日間出芽させた。その後はガラス温室内で栽培管理した。
【００９３】
発病の有無の調査は、播種２１日後（２．５葉期）に下記の調査基準によりイネ籾枯細菌病発病苗数と健全苗数を調査し（１箱当たり約１５０本）、試験例１と同様に発病度を求め、防除価（％）を算出し、評価値に換算した。また、試験例１と同様に、イネに対する薬害の程度についても調査した。
その結果を表３に示す。
発病の調査基準
Ｎ₀： 発病してない苗数
Ｎ₁： 葉身に発病による白化が認められるが、生育は健全苗とほぼ同等の苗数 Ｎ₂： 葉身が発病により白化し、生育が劣る苗数
Ｎ₃： 枯死
【００９４】
【表３】

【００９５】
【試験例３】
（イネ褐条病防除のための種子殺菌効果試験）
供試籾としては、イネ（品種：きらら３９７）籾にイネ褐条病菌（Pseudomonas avenae）の濃厚菌懸濁液（１０⁸／ｍｌ）を減圧接種して得たイネ褐条病菌感染籾を用いた。種子消毒液は実施例２に準じて調製した、表４に示す種々のアミノ酸金属錯化合物の水和剤または対照剤を、水で所定濃度に希釈して調製した。
【００９６】
この薬液中に、上記方法で得られたイネ褐条病菌感染籾を、種籾と薬液との容量比（ｖ／ｖ）が１対１の割合になるようにして加え、２０℃で２４時間にわたり該種籾を浸漬して、消毒した。消毒後の種籾は、２０℃で３日間水に浸種した後、水を切り３０℃で２４時間催芽させた。そして、鳩胸状になった種籾を慣用の箱育苗法に準じてクミアイ粒状培土Ｋ（呉羽化学工業株式会社製）に播種し、３２℃で２日間出芽させた。その後はガラス温室内で栽培管理した。
【００９７】
発病の有無の調査は、播種２１日後（２．５葉期）に下記の調査基準によりイネ褐条病発病苗数と健全苗数を調査し（１箱当たり約１５０本）、試験例１と同様に発病度を求め、防除価（％）を算出し、評価値に換算した。また、試験例１と同様にイネに対する薬害の程度についても調査した。
その結果を表４に示す。
発病の調査基準
Ｎ₀： 発病してない苗数
Ｎ₁： 不完全葉に病斑が認められるが、生育は健全苗とほぼ同等の苗数
Ｎ₂： 葉鞘および葉身に病斑が認められ、生育が劣る苗数
Ｎ₃： 枯死
【００９８】
【表４】

【００９９】
【試験例４】
（イネ苗立枯細菌病防除のための種子消毒効果試験）
供試籾として、イネ籾（品種：きらら３９７）をイネ苗立枯細菌病（Pseudomonas plantarii）の細菌懸濁液中（１０⁶cfu/ml）に減圧接種することによりイネ苗立枯細菌病罹病籾を得た。市販の水酸化銅、塩基性塩化銅を有効成分の一つとする農園芸用殺菌剤を水で所定濃度に希釈した。この殺菌剤希釈液に所定濃度となるようにアミノ酸を添加し、種子消毒液を調製した。
【０１００】
得られた種子消毒液（薬液、浸種水）に、上記方法で得られたイネ苗立枯細菌病罹病種子を、種籾と薬液との容積比が１：１となるようにして、２０℃、２４時間浸漬した。その後、薬液浸漬後の種籾を、種籾と浸種水との容積比が１：２となるように薬液量（浸種水量）を変えて２０℃、３日間浸種した。浸種終了後の種籾は、水を切り３０℃で２４時間蒸気催芽処理し、鳩胸状態になった種籾を慣用の育苗方法に準じて市販の粒状育苗培土（呉羽化学工業株式会社製）に播種し、３２℃で２日間出芽処理した。その後は、ガラス温室で発病管理した。
【０１０１】
以下、上記各試験例と同様に、薬害を評価し、また防除価を算出した。
結果を表５に示す。
【０１０２】
【表５】

【０１０３】
（ ）内数値は、発病度を示す。
水和剤▲３▼：市販製剤；ペフラゾエート＋フルジオキソニル＋塩基性塩化銅水和剤（ペフラゾエート１２％＋フルジオキソニル２％＋塩基性塩化銅７．６％、銅として４．５％含む）
フロアブル▲４▼：市販製剤；イプコナゾール＋水酸化第２銅フロアブル（イプコナゾール５％＋水酸化第２銅４．６％、銅として３％含む）
水酸化第２銅水和剤▲１▼：市販製剤（水酸化第２銅を有効成分とし、銅として１７％含む）
塩基性塩化銅水和剤▲２▼：市販製剤（塩基性塩化剤を有効成分とし、銅として５０％含む）
【０１０４】
【試験例５】
（イネ苗立枯細菌病防除のための種子消毒効果試験）
供試籾として、イネ籾（品種：きらら３９７）をイネ苗立枯細菌病（Pseudomonas plantarii）の細菌懸濁液中（１０⁶cfu/ml）に減圧接種することによりイネ苗立枯細菌病罹病籾を得た。市販の水酸化銅、塩基性塩化銅を有効成分の一つとする農園芸用殺菌剤を水で所定濃度に希釈した。
【０１０５】
得られた種子消毒液（薬液、浸種水）に、上記方法で得られたイネ苗立枯細菌病罹病種子を、種籾と種子消毒液（薬液）との容積比が１：１となるようにして、２０℃、２４時間浸漬した。その後、薬液浸漬後の種籾を、種籾と浸種水との容積比が１：２となるように薬液量を変えて２０℃、３日間水に浸種した。
なお、試験例５において、Ｌ−リジン塩酸塩は、所定濃度になるように▲１▼種籾浸漬直前（種子消毒薬液調整直後）、▲２▼種籾浸種直前（薬液浸漬終了後の浸種開始時の浸種水）、▲３▼浸種２日終了後にそれぞれアミノ酸を添加した。
【０１０６】
浸種終了後の種籾は、水を切り３０℃で２４時間蒸気催芽処理し、鳩胸状態になった種籾を慣用の育苗方法に準じて市販の粒状育苗培土（呉羽化学工業株式会社製）に播種し、３２℃で２日間出芽処理した。その後は、ガラス温室で発病管理した。
以下、上記各試験例と同様に、薬害を評価し、また防除価を算出した。
【０１０７】
結果を表６に示す。
【０１０８】
【表６】

【０１０９】
（ ）内数値は、発病度を示す。
水和剤▲３▼，フロアブル▲４▼，水酸化第２銅水和剤▲１▼，塩基性塩化銅水和剤▲２▼は、前記に同じ。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an agricultural and horticultural seed disinfectant, and more particularly to an agricultural and horticultural seed disinfectant containing an amino acid metal complex compound.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
Rice diseases include fungal diseases caused by filamentous fungi and bacterial diseases caused by bacteria. Traditionally, rice diseases have been treated by fungal diseases such as rice idiot, rice blast, and sesame leaf blight. On the other hand, effective drugs (seed disinfectants) such as benomyl and pefazoate have been developed.
[0003]
In addition to seed disinfectants as described above, seed disinfectants and nursery box disinfectants for bacterial diseases of rice (in this specification, “application” refers to irrigation, soil mixing, spraying, etc. A wide range of use modes including: an inorganic copper disinfectant containing an inorganic copper compound as an active ingredient; an organic copper disinfectant containing an organic copper compound as an active ingredient; a TMTD agent; an oxolinic acid agent; Kasugamycin is widely used. However, these seed disinfectants are not necessarily sufficient for the control of bacterial diseases such as rice seedling blight, or are insufficient in terms of safety to humans, fish and crops, or If it is continuously used, drug-resistant bacteria are generated and there is a problem that a sufficient control effect cannot be exhibited.
[0004]
Therefore, it has been desired to develop a seed disinfectant that is excellent in bacterial diseases of various plants represented by rice, has high safety, and is inexpensive.
As a result of intensive studies by the present inventors in order to solve such problems, the specific amino acid metal complex compound, when used as a seed disinfectant or the like, was excellent in bacterial diseases of various plants including rice. The present invention has been completed by finding out that it can exert a controlling effect and has high safety against crops and livestock.
[0005]
More specifically, the present inventors have found that when a specific amino acid metal complex compound is sprayed on the stems and leaves of grown agricultural and horticultural crops, the crop may be strongly toxic to the crop. However, the petri dish test does not show antibacterial activity against bacterial diseases such as rice seedling blight, but it is extremely useful as a seed disinfectant for rice seeds infected with bacterial pathogens. Thus, there is no phytotoxicity to rice grown after seed disinfection, and it is highly safe for human livestock, and it exhibits excellent medicinal effects only by using a small amount compared to existing seed disinfectants. As a result, the present invention has been completed.
[0006]
The amino acid metal complex is a known compound, and among these amino acid metal complex compounds, methionine, threonine, valine, phenylalanine, isoleucine, proline, glycine, tryptophan, asparagine and glutamine copper complex, or methionine. This nickel complex compound is known as a bactericidal agent (Japanese Patent Publication No. 48-34205) having a controlling effect against citrus ulcer disease, citrus black spot disease, rice blast disease and rice bran disease. In addition to these diseases, a copper complex compound of methionine is known as a bactericidal or disease resistance-providing agent for rice blast, tomato blight and citrus ulcer disease (Japanese Patent Laid-Open No. 47-49548), It is also known as a mildew control agent for grape cultivation (WO95 / 13700) and as a crop growth promoter (DE2217896), and also exhibits anthelmintic activity against porcine parasites (Japanese Veterinary Journal) 24,309,1962) is also known.
[0007]
Further, a copper complex compound of glycine is known as a herbicide (Japanese Patent Laid-Open No. 58-162508). In addition, it is already known that copper complex compounds of various amino acids have antifungal and antibacterial activities [Indian Journal of Physical and Natural Science (Indian J. Phys. Nat. Sci., 3 51, 1983), Journal of Research Pakistan (J. Res. Pak., 5, 7, 1993)].
[0008]
However, it has not been known so far that amino acid metal complex compounds have practically sufficient activity as seed disinfectants such as rice seeds.
[0009]
OBJECT OF THE INVENTION
The present invention is intended to solve the problems associated with the prior art as described above, and has an excellent disinfecting activity on seeds of various plants including rice seeds, and is suitable for crops and livestock. The object is to provide a seed disinfectant for agriculture and horticulture that is highly safe and can be applied to rice seeds and the like.
[0010]
Another object of the present invention is to provide a seed disinfection method that is safe and efficient for crops and human animals.
[0011]
SUMMARY OF THE INVENTION
Seed disinfectant for agricultural and horticultural use according to the present invention,
It is characterized by containing an amino acid metal complex compound represented by the following formula [I] or a salt thereof (collectively referred to as “amino acid metal complex compounds”) as an active ingredient.
[0012]
[Chemical 2]

[0013]
[In the formula [I], R¹, R²Each represents a side chain of an amino acid, which may be the same or different from each other, and M represents any one of copper, zinc, manganese, iron and magnesium. ]
In the present invention, in the above formula [I], R¹, R²These may be any of neutral amino acid side chain, basic amino acid side chain, and acidic amino acid side chain. In the present invention, in the above formula [I], R¹Is a basic amino acid side chain and R²May be an acidic amino acid side chain.
[0014]
Seed disinfectant for agricultural and horticultural use according to the present invention,
(i) a basic, neutral or acidic amino acid or salt thereof;
(ii) a metal or inorganic metal compound;
It is characterized by containing as an active ingredient.
The method for disinfecting seeds according to the present invention comprises an agricultural and horticultural fungicide containing a metal or inorganic metal compound as an active ingredient, water, and a basic, neutral or acidic amino acid or salt thereof simultaneously, or in any order. The seed is disinfected using a seed disinfectant, preferably a seed disinfectant comprising the above-mentioned agricultural and horticultural fungicide and water and the amino acid or salt thereof.
[0015]
In the present invention, in any of the above cases, it is desirable that the inorganic metal compound is at least one of a metal suboxide, a metal hydroxide, and a metal salt.
In the present invention, in any of the above cases, the metal or inorganic metal compound is copper or an inorganic copper compound such as cuprous oxide, copper sulfate, copper chloride, copper hydroxide, basic copper chloride, basic copper sulfate. It is preferable that
[0016]
Such an agricultural and horticultural seed disinfectant according to the present invention has excellent seed disinfecting activity against seeds of various plants including rice seeds, and also has high safety against crops and livestock.
According to the seed disinfecting method according to the present invention, it is possible to disinfect seeds safely and efficiently for crops and human livestock.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the agricultural and horticultural seed disinfectant according to the present invention will be described in detail.
<Amino acid metal complex compounds>
The agricultural and horticultural seed disinfectant according to the present invention contains an amino acid metal complex compound represented by the following formula [I] or a salt thereof (amino acid metal complex compounds), which is a bactericidal active ingredient.
[0018]
[Chemical Formula 3]

[0019]
[In the formula [I], R¹ , R²Each represents a side chain of an amino acid, which may be the same or different from each other, and M represents any one of copper, zinc, manganese, iron and magnesium. ]
Amino acid side chain R¹, R²As a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, particularly preferably 1 to 2 carbon atoms; The alkyl group substituted with a hydroxyl group (hydroxyl group-containing alkyl group); a sulfur-containing alkyl group in which an S atom is interposed between adjacent H—C or C—C in the alkyl group; a hydrogen atom in the alkyl group A carboxyl group-containing alkyl group partially substituted with a carboxyl group; an amino group-containing alkyl group substituted with an amino group; an amide group-containing alkyl group; a part of hydrogen atoms in the alkyl group is an aromatic ring And an aromatic ring-containing alkyl group substituted with a heterocyclic ring-containing alkyl group (or alkylene group). However, carbon numbers of various substituent-containing alkyl groups and alkyl groups in the alkylene group are all the same as in the case of the alkyl group (the same applies hereinafter).
[0020]
Amino acid side chain R¹, R²Examples of hydrogen atom or alkyl group include hydrogen atom derived from glycine, CH derived from alanine_Three-, (CH derived from valine)_Three)₂CH-, derived from leucine (CH_Three)₂CHCH₂-, C derived from isoleucine₂H_FiveCH (CH_ThreeAmong these, the amino acid side chain R¹, R²Is preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms or 2 or less carbon atoms because it becomes an amino acid metal complex compound having excellent water solubility and excellent seed disinfection effect.
[0021]
Examples of the hydroxyl group-containing alkyl group include serine-derived HOCH.₂-, Threonine-derived CH_ThreeCH (OH)-and the like.
Examples of the sulfur-containing alkyl group include cysteine-derived HSCH.₂-HOOC derived from cystine (NH₂) CHCH₂SSCH₂-, CH derived from methionine_ThreeS (CH₂)₂-Etc. are mentioned.
[0022]
As the carboxyl group-containing alkyl group, HOOCCH derived from an acidic amino acid aspartic acid₂-HOOC derived from the acidic amino acid glutamic acid (CH₂)₂-Etc. are mentioned.
An amino group-containing alkyl group (excluding those having an amide group, including those having both a hydroxyl group and an amino group, those having an amino group and an S atom, and those having a guanidyl group) H from lysine₂N (CH₂)_Four-H derived from the basic amino acid arginine₂NC (= NH) NH (CH₂)_Three-, Ornithine-derived H₂N (CH₂)_Three-, H derived from hydroxylysine₂NCH₂CH (OH) (CH₂)₂-, H derived from thialysine₂N (CH₂) SCH₂-, H derived from diaminobutyric acid₂N (CH₂)₂-, H derived from diaminopropionic acid₂NCH₂-Etc. are mentioned.
[0023]
Examples of the amide group-containing alkyl group include H derived from glutamine.₂NCO (CH₂)₂-, H from asparagine₂NCOCH₂-Etc. are mentioned.
As the aromatic ring-containing alkyl group, Ph-CH derived from phenylalanine₂-(However, Ph: phenyl group), HO-Phe-CH derived from tyrosine₂-(However, Phe: phenylene group) etc. are mentioned.
[0024]
As the heterocycle-containing alkyl group (or alkylene group), the basic amino acid histidine-derived Imi-CH₂-(However, Imi: imidazole ring), Indo-CH derived from tryptophan₂-(However, Indo: indole ring),-(CH derived from proline₂)_Three-, -CH derived from oxyproline₂CH (OH) CH₂-Etc. are mentioned.
[0025]
R as described above¹, R²Among them, an amino acid metal complex compound having excellent water solubility and excellent seed disinfection effect can be obtained.¹, R²Is a hydrogen atom, an alkyl group having 3 or less carbon atoms, further 2 or less; a hydroxyl group-containing alkyl group; a carboxyl group-containing alkyl group; an amino group-containing alkyl group (except for those having an amide group, Amide group-containing alkyl group; tyrosine-derived HO-Ph-CH among aromatic ring-containing alkyl groups₂-(However, Ph: phenylene group); Imi-CH derived from histidine among heterocycle-containing alkyl groups (or alkylene groups)₂-(However, Imi: Imidazole ring),-(CH derived from proline₂)_Three-, -CH derived from hydroxyproline₂CH (OH) CH₂-Is preferred.
[0026]
Among these, amino acid side chain R¹, R²In particular, hydrogen atoms derived from glycine and CH derived from alanine_Three-HOCH derived from serine₂-, H derived from Lysine₂N (CH₂)_Four-, H derived from arginine₂NC (= NH) NH (CH₂)_Three-, Ornithine-derived H₂N (CH₂)_Three-, H derived from hydroxylysine₂NCH₂CH (OH) CH₂CH₂-, H derived from thialysine₂N (CH₂) SCH₂-, H derived from diaminobutyric acid₂N (CH₂)₂-, H derived from diaminopropionic acid₂NCH₂-, -CH derived from hydroxyproline₂CH (OH) CH₂-Is preferred.
[0027]
As such an amino acid metal complex compound [I], specifically, as summarized in Table 1, for example, in the above formula [I], R¹, R²Asparagine side chain (H₂NCO-CH₂-) And M is copper, bis-L-asparagine copper complex compound (Compound No. 1),
R¹, R²Are both alanine side chains (CH_Three-) And M is copper, a bis-L-alanine copper complex compound (Compound No. 2) or a bis-β-alanine copper complex (Compound No. 3),
R¹, R²Is the isoleucine side chain (C₂H_FiveCH (CH_Three)-), And M is copper, bis-L-isoleucine copper complex compound (Compound No. 5),
R¹, R²Is a glycine side chain (H) and M is copper, a bis-glycine copper complex compound (Compound No. 7),
R¹, R²Are both glutamine side chains (H₂N (CO)-(CH₂)₂-) And M is copper, bis-L-glutamine copper complex compound (Compound No. 8),
R¹, R²Are both serine side chains (HOCH₂-) And M is copper, a bis-L-serine copper complex compound (Compound No. 11),
R¹, R²Are both tryptophan side chains [Indo-CH₂-(Where Indo: indole ring)], and M is copper, a bis-L-tryptophan copper complex compound (Compound No. 12),
R¹, R²Are both threonine side chains [CH_ThreeCH (OH)-] and M is copper, a bis-L-threonine copper complex compound (Compound No. 14),
R¹, R²Are both valine side chains [(CH_Three)₂CH-] and M is copper, a bis-L-valine copper complex compound (Compound No. 15),
R¹, R²Are both hydroxyproline side chain [-CH₂CH (OH) CH₂-] And M is copper, bis-L-hydroxyproline copper complex compound (Compound No. 17),
R¹, R²Are both proline side chains [-(CH₂)_Three-] And M is copper, bis-L-proline copper complex compound (Compound No. 19),
R¹, R²Are both phenylalanine side chains [Ph-CH₂-(Where Ph: phenyl group)], and M is copper, a bis-L-phenylalanine copper complex compound (Compound No. 20),
R¹, R²Are both lysine side chains [H₂N (CH₂)_Four-] And M is copper, a bis-L-lysine copper complex compound (Compound No. 21),
R¹, R²Are both leucine side chains [(CH_Three)₂CHCH₂-], And bis-L-leucine copper complex compound (Compound No. 30) in which M is copper.
[0028]
In addition, as a salt of such amino acid metal complex compound [I] (metal complex compound of amino acid salt), in the case of basic amino acid metal complex compound, inorganic acid salt, organic acid salt, fatty acid salt and anionic surface activity A chemical salt is used.
Examples of the inorganic acid include hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, and carbonic acid. Examples of the organic acid include acetic acid, benzoic acid, sorbic acid, glycolic acid, lactic acid, tartaric acid, and succinic acid. Examples of the fatty acid include caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, coconut oil fatty acid, and beef tallow fatty acid. Examples of the anionic surfactant include lauryl sulfate, lauryl ether sulfate, and dodecylbenzene sulfonic acid.
[0029]
In the case of an acidic amino acid metal complex compound, sodium salts, potassium salts, calcium salts and the like of the above acidic amino acids may be mentioned.
In addition, a metal complex compound of a salt of a basic amino acid and an acidic amino acid, in which one of the amino acid side chains of the metal complex compound is a basic amino acid side chain and the other is an acidic amino acid side chain.
[0030]
Specific examples of the salt of such an amino acid metal complex compound [I] include, for example, R in the above formula [I].¹, R²Are both arginine side chains [H₂NC (= NH) NH (CH₂)_Three-] And M is copper, a hydrochloride of a bis-L-arginine copper complex compound (bis-L-arginine monohydrochloride copper complex compound: Compound No. 4),
R¹, R²Ornithine side chain [H₂N (CH₂)_Three-] And M is copper, a hydrochloride of a bis-L-ornithine copper complex compound (bis-L-ornithine monohydrochloride copper complex compound: Compound No. 6),
R¹, R²Are both L-2,4-diaminobutyric acid side chain [H₂N- (CH₂)₂-], And M is copper. Hydrochloride of bis-L-2,4-diaminobutyric acid (DABA) copper complex compound (bis-L-2,4-diaminobutyric acid (DABA) · monohydrochloride copper Complex compound: Compound No. 9),
R¹, R²Are both DL-2,3-diaminopropionic acid (DAPA) side chain [H₂N-CH₂-], And M is copper bis-DL-2,3-diaminopropionic acid (DAPA) copper complex hydrochloride (bis-DL-2,3-diaminopropionic acid (DAPA) monohydrochloride copper Complex compound: Compound No. 10),
R¹, R²Are both L-4-thiaridine side chain [H₂N (CH₂)₂SCH₂-] And M is copper, a hydrochloride of a bis-L-4-thalizine copper complex compound (bis-L-4-thalizine monohydrochloride copper complex: Compound No. 13),
R¹, R²Are both histidine side chains [Imi-CH₂-(Where Imi: imidazole ring)], and M is copper, a hydrochloride of a bis-L-histidine copper complex compound (bis-L-histidine monohydrochloride copper complex: Compound No. 16),
R¹, R²Are both hydroxy lysine side chains [H₂NCH₂CH (OH) (CH₂)₂-] And M is copper, a hydrochloride salt of a bis-DL-hydroxylysine copper complex compound (bis-DL-hydroxylysine monohydrochloride copper complex: Compound No. 18),
R¹, R²Are both lysine side chains [H₂N (CH₂)_Four-] And M is copper, hydrochloride of bis-L-lysine copper complex compound (bis-L-lysine monohydrochloride copper complex compound: Compound No. 22),
R¹, R²Are both lysine side chains [H₂N (CH₂)_Four-] And M is copper, bis-L-lysine copper complex hydrogen carbonate (bis-L-lysine · 1 hydrogen carbonate copper complex: Compound No. 23),
R¹, R²Are both lysine side chains [H₂N (CH₂)_Four-] And M is copper, a dodecylbenzenesulfonic acid (DBSA) salt of a bis-L-lysine copper complex compound (bis-L-lysine / DBSA salt copper complex compound: Compound No. 24),
R¹, R²Are both lysine side chains [H₂N (CH₂)_Four-] And M is copper, lauric acid (LauA) salt of bis-L-lysine copper complex compound (bis-L-lysine / LauA salt copper complex compound: Compound No. 25),
R¹, R²Are both lysine side chains [H₂N (CH₂)_Four-] And M is copper, hydrochloride of bis-D-lysine copper complex compound (bis-D-lysine monohydrochloride copper complex compound: Compound No. 26),
R¹, R²Are both lysine side chains [H₂N (CH₂)_Four-] And M is copper, hydrochloride of bis-DL-lysine copper complex compound (bis-DL-lysine monohydrochloride copper complex compound: Compound No. 27),
R¹, R²Are both lysine side chains [H₂N (CH₂)_Four-], And M is zinc, a hydrochloride salt of a bis-L-lysine zinc complex compound (bis-L-lysine monohydrochloride zinc complex compound: Compound No. 31),
R¹, R²Are both lysine side chains [H₂N (CH₂)_Four-], And hydrochloride of a bis-L-lysine magnesium complex compound (bis-L-lysine · monohydrochloride magnesium complex compound: Compound No. 32) in which M is magnesium.
[0031]
In the above formula [I], R¹, R²Are different from each other in the above formula [I].¹Is the lysine side chain [H_ThreeN⁺(CH₂)_Four−] And R²Is aspartic acid side chain [^-OOCCH₂-] And M is copper, a copper complex compound of L-lysine · L-aspartate (L-lysine · L-aspartate copper complex: compound No. 28),
In the above formula [I], R¹Is the lysine side chain [H_ThreeN⁺(CH₂)_Four−] And R²Is the glutamic acid side chain [^-OOC- (CH₂)₂-], And M is copper, a copper complex compound of L-lysine · L-glutamate (L-lysine · L-glutamate copper complex: Compound No. 29) and the like.
[0032]
One or more of such amino acid metal complex compounds may be contained in the agricultural and horticultural seed disinfectant of the present invention.
The amino acid metal complex compounds [I] exemplified above are shown together in Table 1.
Among such amino acid metal complex compounds, numbers 1, 4-7, 9-11, 13-14, 16-19, 21-27 in Table 1 below are preferable, and numbers 4, 6- 7, 9-11, 13, 17-18, 21-27 are preferable because they are excellent in water solubility and particularly excellent in the seed disinfection effect.
[0033]
[Table 1]

[0034]
This compound number is also referred to in Examples and Test Examples described later.
In the above formula [I], R¹And R²In complex compounds different from, R¹Is a basic amino acid side chain and R²When a salt is formed as in the case where is an acidic amino acid side chain, a single complex compound is stably obtained.
In the present invention, in the above formula [I], R¹Is a basic amino acid side chain and R²An amino acid metal complex compound in which is an acidic amino acid side chain (metal complex compound of an acidic amino acid salt of a basic amino acid) is represented by the following formula [II].
[0035]
[Formula 4]

[0036]
[In the formula [II], R^ThreeIndicates a side chain of a basic amino acid, R^FourRepresents a side chain of an acidic amino acid, and M represents any one of copper, zinc, manganese, iron and magnesium. ]
As such a metal complex compound [II], among the amino acid metal complex compounds [I] exemplified above, L-lysine · L-aspartate copper complex compound (Compound No. 28) and L-lysine · The L-glutamate copper complex compound (Compound No. 29) is included in the compound represented by the formula [II], that is, the metal complex compound of an acidic amino acid salt of a basic amino acid.
[0037]
That is, L-lysine · L-aspartate copper complex compound (Compound No. 28) is represented by the basic amino acid side chain R in the formula [II]:^ThreeIs the lysine side chain [H_ThreeN⁺(CH₂)_Four-], And the acidic amino acid side chain R^FourIs aspartic acid side chain [^-OOCCH₂−] And corresponds to a complex compound in which M is copper.
The L-lysine / L-glutamate copper complex compound (Compound No. 29) is represented by the basic amino acid side chain R in the above formula [II].^ThreeIs the lysine side chain [H_ThreeN⁺(CH₂)_Four-], And the acidic amino acid side chain R^FourIs the glutamic acid side chain [^-OOC (CH₂)₂−] And corresponds to a complex compound in which M is copper.
<Production of amino acid metal complex compounds>
The amino acid metal complex compound represented by the above formula [I] or [II] or a salt thereof (amino acid metal complex compounds) can be produced by a conventionally known method described in the above-mentioned literature.
[0038]
For example, in the formula [I], the amino acid copper complex compound [Ia] in which M is copper, as shown in the following reaction formula, converts the basic copper carbonate into an aqueous solution of various amino acids (a) as copper with respect to the amino acid. In addition to being 1/2 equivalent, it can be suitably produced by reacting by heating as necessary. Instead of the basic copper carbonate, cuprous oxide, copper sulfate, copper chloride, copper hydroxide, basic copper chloride, or basic copper sulfate may be used.
[0039]
[Chemical formula 5]

[0040]
[In formula (a), R¹Represents an amino acid side chain as described above. ]
In addition, in the formula [II], the amino acid copper complex compound [II-a] in which M is copper is a free basic amino acid (a-2) and an acidic amino acid (a-3) as shown in the following formula: Are dissolved in water in an equimolar amount to prepare an acidic amino acid salt solution of a basic amino acid. To this aqueous solution, basic copper carbonate is added to make a half equivalent of copper to the amino acid, and if necessary, By heating and reacting, a copper complex compound [II-a] of an acidic amino acid salt of a basic amino acid can be preferably produced.
[0041]
[Chemical 6]

[0042]
[However, in the above reaction formula, R^ThreeIndicates a basic amino acid side chain and R^FourIndicates an acidic amino acid side chain. ]
In the above formula [II], an amino acid complex compound in which M is a metal other than copper can also be produced in the same manner as described above. The amino acids (a-2), (a-3) and the basic copper carbonate (CuCO_Three・ Cu (OH)₂ ・ H₂Any metal compounds such as O) are known substances, and commercially available products may be used.
[0043]
Examples of amino acids used in the above reaction include neutral amino acids, basic amino acids, acidic amino acids and the like. Specific examples of neutral amino acids include asparagine, alanine, isoleucine, glycine, glutamine, serine, tyrosine, tryptophan, threonine, valine, hydroxyproline, phenylalanine, proline, methionine, and leucine.
Among these, alanine, isoleucine, glycine, serine, tyrosine, threonine, valine, hydroxyproline, proline, and methionine are preferably used in consideration of the seed disinfection effect of the obtained compound.
[0044]
Examples of basic amino acids include arginine, histidine, lysine, hydroxylysine, ornithine, 2,4-diaminobutyric acid, 2,3-diaminopropionic acid, 4-thialysine, and the like.
Among these, considering the seed disinfection effect of the resulting compound, 2,4-diaminobutyric acid, arginine, lysine, hydroxylysine, ornithine, 2,3-diaminopropionic acid, and 4-thiadiline are preferably used. .
[0045]
Examples of acidic amino acids include aspartic acid and glutamic acid.
In addition, as said basic amino acid, the free thing or inorganic acid salt, organic acid salt, fatty acid salt, and anionic surfactant salt can also be used. Examples of the inorganic acid include hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, and carbonic acid. Examples of the organic acid include acetic acid, benzoic acid, sorbic acid, glycolic acid, lactic acid, tartaric acid, and succinic acid. Examples of the fatty acid include caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, coconut oil fatty acid, and beef tallow fatty acid. Examples of the anionic surfactant include lauryl sulfate, lauryl ether sulfate, and dodecylbenzene sulfonic acid.
[0046]
In addition, as the acidic amino acid, a free substance or a metal salt thereof can be used. This metal includes sodium, potassium and calcium.
The amino acid used for producing the amino acid metal complex compounds may be an optically active L-form or D-form, or an optically inactive racemate. Of these, basic amino acids such as lysine and ornithine are particularly suitable for enhancing the bactericidal effect. In producing the above-mentioned amino acid metal complex compounds, in addition to the simple substance of metal M, the suboxide of the metal, the hydroxide of the metal, sulfate, hydrochloride, nitrate, carbonate of these metals , Acetate, oxalate and the like can be used. Examples of the metal M include copper, zinc, manganese, iron, and magnesium. In the amino acid metal complex compound used in the present invention, as is apparent from the above formula [I], the bond molar ratio of amino acid to metal is preferably 2: 1.
[0047]
In addition, a salt of an amino acid metal complex compound (metal complex of an amino acid salt) is, for example,
It can be obtained by reacting an amino acid salt such as L-lysine monohydrochloride with a metal source such as cuprous oxide, basic copper carbonate, etc., if necessary.
<Seed disinfectant for agriculture and horticulture>
The seed disinfectant for agricultural and horticultural use according to the present invention contains the amino acid metal complex compounds as active ingredients. The content of the amino acid metal complex compounds depends on the dosage form of the disinfectant, its method of use, etc. Although it can change suitably according to these conditions and it does not restrict | limit in particular, Usually, it is about 0.1 to 95 weight%.
[0048]
The seed disinfectant for agriculture and horticulture according to the present invention may contain one or more of the above amino acid metal complex compounds.
Further, the agricultural and horticultural seed disinfectant according to the present invention includes other known active compounds in addition to the above amino acid metal complex compounds, such as fungicides, insecticides, acaricides, nematicides, insect growth It may contain regulators, herbicides, bird repellents, plant growth regulators, fertilizers, soil conditioners, and the like. In this way, the agricultural and horticultural seed disinfectant containing amino acid metal complex compounds and other active compounds can expand the scope of application (applicable disease, method of use, time of use, etc.), and in some cases compounded Synergistic effects of various active ingredients can also be expected.
[0049]
In the present invention, an amino acid [amino acid capable of forming an amino acid metal complex compound represented by the above formulas (a), (a-2), (a-3)] and a metal (in the above amino acid metal complex compound) Or a metal compound similar to that contained in the formulation, preferably in a stoichiometric amount, that is, a molar ratio of 2: 1, and mixed with the above amino acid by diluting the formulation with water at the time of use. It can also be used as an agricultural and horticultural seed disinfectant that produces metal complex compounds.
[0050]
Examples of the metal compound used in this case include metal suboxides; metal hydroxides; metal salts such as sulfates, hydrochlorides, nitrates, carbonates, acetates, and oxalates.
Examples of the metal include copper, zinc, manganese, iron, magnesium, etc. Among them, copper is preferable. Examples of copper-based inorganic compounds (inorganic copper compounds) include cuprous oxide, copper sulfate, copper chloride, copper hydroxide, basic copper chloride, and basic copper sulfate.
[0051]
Moreover, the enhancement effect of a seed disinfection activity can be anticipated by mixing the existing agricultural chemical formulation which uses copper or the said inorganic copper compound as an active ingredient, and the said amino acid.
The seed disinfectant for agricultural and horticultural purposes according to the present invention is not particularly limited as long as it contains the amino acid metal complex compounds as active ingredients, and various agents can be used according to conventionally known formulations depending on the purpose of use. Molds can be prepared.
[0052]
For example, an amino acid metal complex compound, various carriers as described later, a surfactant, and other adjuvants for formulation are blended, and for example, a wettable powder, a granule wettable powder, an emulsion, and a liquid drug are prepared by a conventional method. , And can be formulated into various dosage forms such as flowable agents, fine granules, granules, and seed coating agents.
As described above, carriers used for producing various types of agricultural and horticultural seed disinfectants include solid carriers and liquid carriers. Among these carriers, examples of solid carriers include kaolin, bentonite, clay, Montmorillonite, talc, vermiculite, attapul guide, diatomaceous earth, silica sand, synthetic silicate, calcium carbonate, calcium phosphate, alumina, white carbon, ammonium sulfate, urea, starch, crystalline cellulose, soy flour, walnut flour, tobacco stem powder, etc. .
[0053]
Examples of the liquid carrier include water, alcohols (eg, methanol, ethanol, isopropyl alcohol, ethylene glycol, glycerol, etc.), ethers (eg, dioxane, tetrahydrofuran, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), Examples include esters (eg, glycerin esters of fatty acids), sulfoxides (eg: dimethyl sulfoxide), aliphatic or alicyclic hydrocarbons (eg: cyclohexane, paraffins, etc.), and the like.
[0054]
Examples of the surfactant include anionic surfactants such as alkyl sulfate ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphates;
Nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan acid esters;
Etc.
[0055]
Examples of the formulation adjuvant include physical property improvers, carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), gum arabic, gelatin, casein, sodium alginate, tragacanth gum, xanthan gum and the like as a binder. Can be mentioned.
<How to use seed disinfectant for agriculture and horticulture>
The agricultural and horticultural seed disinfectant according to the present invention is used in accordance with conventional methods according to its dosage form, application (eg, for seed disinfection and nursery box application), applicable disease, time of use, and the like.
[0056]
  In the present invention, an amino acid and a metal are used in advance.CompoundA compound comprising a product or a salt thereof is prepared, and when this compound is used, the compound is diluted with water to form an amino acid metal complex and used as a seed disinfectant for agriculture and horticulture according to the present invention. May be. Further, in the present invention, an existing agricultural chemical formulation containing the above metal or a metal compound such as a hydroxide of the metal, for example, copper hydroxide, basic copper chloride, basic copper sulfate, etc. as an active ingredient is added to lysine or the like. An amino acid metal complex compound can be formed by adding an amino acid and diluting with water, and can also be used as a seed disinfectant for agriculture and horticulture. In this case, the amino acid may be used in a stoichiometric amount of 2 moles with respect to 1 mole of metal, but is usually used in an amount of 0.1 to 2.5 moles.
[0057]
In addition, when adding an amino acid, preparation of a chemical solution of an existing agricultural chemical formulation containing the above metal or a metal compound such as a hydroxide of the metal, for example, copper hydroxide, basic copper chloride, basic copper sulfate, etc. as an active ingredient It is not limited to the time, for example, after preparation of the existing agricultural and horticultural fungicide, it may be before soaking, may be during the soaking period, and before any end of the soaking period, at any time Can also be added at once, or can be added in small portions in multiple portions. Alternatively, the seed sterilized seed pods may be soaked in a liquid containing amino acids.
[0058]
The method of using the agricultural and horticultural seed disinfectant according to the present invention will be described in more detail. The application of the disinfectant is not particularly limited, and it is used for any purpose such as seed disinfection and nursery box application. be able to. The amount of seed disinfectant used for agricultural and horticultural use depends on the type of amino acid metal complex compound and other medicinal ingredients contained in the active ingredient, the target of application (for example, target crops, target diseases, the state of their occurrence, etc.) It can be changed as appropriate.
[0059]
For example, in order to use the agricultural and horticultural seed disinfectant of the present invention as a rice seed disinfectant, it suffices to follow a general method for using a seed disinfectant. More specifically, in agricultural and horticultural seed disinfectants used in liquid form such as wettable powders, emulsions, flowable powders, and granular wettable powders, the active ingredient concentration is 50 to 50000 ppm by diluting the disinfectant with water or the like. The rice seed meal may be immersed in this chemical solution for 10 to 60 minutes (short-time immersion) or 24 to 48 hours (long-time immersion), preferably at 200 to 20000 ppm.
[0060]
In addition, preparations used in liquid form (excluding emulsions) such as wettable powders, flowable powders, and granular wettable powders, except for emulsions, are diluted with water or the like as necessary to obtain 1 to 5% by weight of seed weight. The seeds may be sprayed in an amount (0.5-20 g as an active ingredient amount / kg of seed weight), and the seeds may be smeared uniformly using a mortar mixer or the like so as to obtain such an amount. Also good.
[0061]
In addition, a solid preparation such as a wettable powder is coated on the surface of seeds in an amount of 0.1 to 2% by weight of the seed weight (0.5 to 20 g as an active ingredient amount / kg of seed weight). It may be used.
When spraying the agricultural and horticultural seed disinfectant according to the present invention in a nursery box (size: length x width x height = 60 cm x 30 cm x 3 cm), dilute the wettable powder, emulsion, flowable agent in water, The active ingredient concentration is set to 100 to 10000 ppm, preferably 400 to 40000 ppm, and this chemical solution is sprayed in an amount of 20 to 200 ml / nursery box from above the seedling box after sowing rice seed pods, or using a watering can For example, a method of irrigating with an amount of 200 to 1000 ml / nursing box can be employed.
[0062]
In addition, when the agricultural and horticultural seed disinfectant according to the present invention is a powder, a granule, etc., it is directly applied to the spreader by hand from above the seedling box after sowing or after covering the rice seed pod. Alternatively, a method of spraying in an amount of 5 to 50 g / nursing box (as an active ingredient, 0.1 to 10 g / nursing box) may be employed.
[0063]
【The invention's effect】
The agricultural and horticultural seed disinfectant according to the present invention has an excellent disinfecting activity for various seeds including rice seeds. This seed disinfectant is used as a rice seed disinfectant and a rice seedling box disinfectant. In particular, the present invention exhibits a stable and high seed disinfection effect against rice seedling blight, rice blight and rice brown streak, and can effectively control these diseases.
[0064]
In addition, the amino acid metal complex compounds as active ingredients contained in the agricultural and horticultural seed disinfectant according to the present invention have extremely low toxicity (oral:> 1000 mg / kg). Since the active ingredient of the seed disinfectant for agricultural and horticultural use of the present invention is an amino acid metal complex compound or the like, the amount of metal used when synthesizing this complex compound, for example, copper, is suppressed to less than half the amount of conventional drugs. The other component, the amino acid, is also biodegradable and has little environmental pollution.
[0065]
【Example】
Next, the agricultural and horticultural seed disinfectant of the present invention, examples of its use, and production examples of amino acid metal complex compounds contained in the agricultural and horticultural seed disinfectant will be described in more detail. There are no restrictions.
In Examples and Production Examples, (parts) are all parts by weight, and% is% by weight.
[0066]
[Production Example 1]
(Bis-L-serine copper complex compound, Compound No. 11)
5.000 g (47.58 mmol) of L-serine was dissolved in 10 ml of distilled water, and 5.678 g (23.79 mmol) of basic copper carbonate was gradually added thereto so as not to cause bumping. The resulting mixture was heated and stirred at 60 ° C. for 30 minutes and then filtered. The insoluble matter remaining on the filter paper was washed with 5 ml of hot water, and this washing solution and the filtrate were combined. The combined filtrate was concentrated under reduced pressure to a semi-solid state, 10 ml of methanol was added and dissolved by heating at 60 ° C. When this was left at room temperature, crystals immediately precipitated. The crystals were collected by filtration and dried under reduced pressure to obtain 6.402 g (yield 87.45%) of a copper complex compound of L-serine.
[0067]
IR (KBr diffuse reflection method): 3344,3255,3213,3132,2937,1664,1631,1606,1394,1328,1276,1164,1099,1058,985,707cm^-1
[0068]
[Production Example 2]
(Bis-L-lysine / monohydrochloride copper complex compound, Compound No. 22)
L-lysine monohydrochloride (5.000 g, 27.37 mmol) was dissolved in 10 ml of distilled water, and 0.979 g (6.84 mmol) of cuprous oxide was added thereto. The obtained mixture was heated and stirred at 60 ° C. for 12 hours, and then filtered. The insoluble material was washed with 5 ml of hot water, and the washing and the filtrate were combined. The combined filtrate was concentrated under reduced pressure to a semi-solid state, 10 ml of methanol was added and dissolved by heating at 60 ° C. When this was left at room temperature, crystals immediately precipitated. The crystals were collected by filtration and dried under reduced pressure to obtain 6.018 g (yield 95.04%) of a copper complex compound of L-lysine monohydrochloride.
[0069]
IR (KBr diffuse reflection method): 3444,3259,3010,2941,1660,1584,1523,1392,1134cm^-1
[0070]
[Production Example 3]
(Bis-L-lysine / 1 hydrogencarbonate copper complex compound, Compound No. 23)
L-lysine (free base) (5.000 g, 34.20 mmol) was dissolved in 10 ml of distilled water, and 4.082 g (17.10 mmol) of basic copper carbonate was gradually added thereto so as not to cause bumping. The obtained mixture was heated and stirred at 60 ° C. for 30 minutes, and then carbon dioxide gas was aerated for 2 hours with stirring at room temperature to adjust the pH to 7.0. After filtration, the insoluble material was washed with 5 ml of hot water, and this washing solution and the filtrate were combined. The combined filtrate was concentrated under reduced pressure to a semi-solid state, 10 ml of methanol was added and dissolved by heating at 60 ° C. When this was left at room temperature, crystals immediately precipitated. The crystals were collected by filtration and dried under reduced pressure to obtain 4.988 g (yield: 78.93%) of a copper complex compound of L-lysine hydrogencarbonate.
[0071]
IR (KBr diffuse reflection method): 3220,2968,2869,1643,1458,1359,1240,1199,1083,918,877,767,700cm^-1
[0072]
[Production Example 4]
(Bis-L-ornithine monohydrochloride copper complex compound, Compound No. 6)
L-ornithine (free base) (5,000 g, 37.83 mmol) was dissolved in 10 ml of distilled water, and 2.543 g (18.92 mmol) of copper chloride was added thereto. The obtained mixture was heated and stirred at 60 ° C. for 30 minutes, and then concentrated under reduced pressure until it became a semi-solid state. To this, 10 ml of hot methanol was added and dissolved by heating at 60 ° C. When this was left at room temperature, crystals immediately precipitated. The crystals were collected by filtration and dried under reduced pressure to obtain 8.184 g (yield 96.4%) of a copper complex compound of L-ornithine monohydrochloride.
[0073]
IR (KBr diffuse reflection method): 3396,3232,3012,1625,1593,1523,1400,1344,1134,1053,813,648cm^-1
[0074]
[Production Example 5]
(L-lysine / L-glutamate copper complex compound, Compound No. 29)
L-lysine (free base) (2.000 g, 13.68 mmol) and L-glutamic acid (2.013 g, 13.68 mmol) were dissolved in distilled water (10 ml), and basic copper carbonate (3.266 g, 13.68 mmol) was suddenly boiled. Gradually added to prevent it. The resulting mixture was heated and stirred at 60 ° C. for 30 minutes and then filtered. The insoluble material was washed with 5 ml of hot water, and the washing and the filtrate were combined. The combined filtrate was concentrated under reduced pressure to a semi-solid state, 10 ml of methanol was added and dissolved by heating at 60 ° C. Next, when it was left overnight in a refrigerator, crystals precipitated. The crystals were collected by filtration and dried under reduced pressure to obtain 4.524 g (yield 84.62%) of a copper complex compound of L-lysine / L-glutamate.
[0075]
IR (KBr diffuse reflection method): 3280,3242,3028,2945,2862,1618,1556,1504,1398,1334,1145,1058,798,659cm^-1
[0076]
[Example 1]
(Wettable powder)
30 parts of bis-L-lysine monohydrochloride copper complex compound (Compound No. 22), 3 parts of sodium alkylbenzene sulfonate, 5 parts of polyoxyethylene nonylphenyl ether and 62 parts of clay are mixed and pulverized uniformly. A wettable powder containing 30% of the components was obtained.
[0077]
[Example 2]
(emulsion)
30 parts of a bisglycine copper complex compound (Compound No. 7), 55 parts of methyl ethyl ketone and 15 parts of polyoxyethylene nonylphenyl ether were mixed and dissolved to obtain an emulsion containing 30% of the active ingredient.
[0078]
[Example 3]
(Granule)
Uniformly mixing 5 parts of bis-L-ornithine monohydrochloride copper complex compound (Compound No. 6), 1.5 parts of lauryl sulfate, 1.5 parts of calcium lignin sulfonate, 25 parts of bentonite and 67 parts of clay, After adding 15 parts of water to this and kneading with a kneader, it was granulated with a granulator and dried with a fluid dryer to obtain a granule containing 5% of the active ingredient.
[0079]
[Example 4]
(Flowable agent)
40 parts of bis-L-alanine copper complex compound (Compound No. 2), 2 parts of lauryl sulfate, 2 parts of sodium alkylnaphthalene sulfonate, 1 part of hydroxypropylcellulose and 55 parts of water are mixed uniformly, and the active ingredient is 40%. The contained flowable agent was obtained.
[0080]
[Example 5]
(Wettable powder)
23.4 parts of L-arginine monohydrochloride, 6.6 parts of basic copper carbonate, 3 parts of sodium alkylbenzenesulfonate, 55 parts of polyoxyethylene nonylphenyl ether and 62 parts of clay are uniformly mixed and pulverized. A balm was obtained. When this wettable powder is diluted with water at the time of use, an equivalent component containing 28.8% of bis-L-arginine · monohydrochloride copper complex compound (Compound No. 4) as an active ingredient is formed.
[0081]
Next, although the test example of the control activity with respect to various plant diseases of the seed disinfectant for agricultural and horticultural purposes according to the present invention is shown, the present invention is not limited to the following test examples.
[0082]
[Test Example 1]
(Seed disinfection effect test for controlling rice seedling blight)
As test pods, a concentrated bacterial suspension of rice seedlings (Pseudomonas plantarii) at the flowering stage of rice (variety: Kirara 397) (10^Four/ Ml) was used to inoculate rice seedlings with bacterial disease infection.
[0083]
Seed disinfecting solutions (chemical solutions) were prepared according to Example 2 by diluting wettablets or control agents of various amino acid metal complex compounds shown in Table 2 to a predetermined concentration with water.
To this chemical solution, the rice seedling bacteriomycetes-infected rice cake obtained by the above-described method was added so that the volume ratio (v / v) of the seed rice to the chemical solution became a ratio of 1: 1, and 24 ° C. at 24 ° C. The seed pods were immersed and disinfected over time. The disinfected seed pods were immersed in water at 20 ° C. for 3 days, then drained and germinated at 30 ° C. for 24 hours. Then, the seed pods in the form of pigeon breasts were sown on Kumiai granular cultivated soil K (manufactured by Kureha Chemical Co., Ltd.) according to a conventional box raising method, and germinated at 32 ° C. for 2 days. Thereafter, the cultivation was managed in a glass greenhouse.
[0084]
The investigation of the presence or absence of disease was conducted 21 days after sowing (2.5 leaf stage) by investigating the number of seedlings with healthy rice seedlings and the number of healthy seedlings according to the following survey criteria (about 150 per box). The disease severity was determined by equation (1).
Survey criteria for disease onset
N₀: Number of seedlings not affected
N₁： Number of seedlings with whitening or yellowing due to disease
N₂: Number of seedlings whose leaf blades are whitened due to disease
N_Three: Withering
[0085]
[Expression 1]

[0086]
This test was conducted in 1 district, 3 continuous systems, the average disease severity was calculated, and the control value (%) was obtained from the following formula. This control value was converted into an evaluation value of the control effect according to the following criteria.
The results are shown in Table 2.
[0087]
[Expression 2]

[0088]
Evaluation value of control effect Control value
5 95% or more
4 Less than 90-95%
3 Less than 70-90%
2 Less than 40-70%
1 Less than 40%
Moreover, about the phytotoxicity with respect to rice, the budding state, the growth degree, etc. were observed, and it displayed on the basis of the following phytotoxicity investigation index.
[0089]
The test results are summarized in Table 2.
Investigation index of drug damage
5: Excitement, 4: Acupuncture, 3: Many, 2: Slight, 1: Slight, 0: None
[0090]
[Table 2]

[0091]
[Test Example 2]
(Seed disinfection effect test for controlling bacterial wilt of rice)
As a test meal, a concentrated bacterial suspension of rice (variety: Kirara 397) and a rice bacterial bacterium (Pseudomonas glumae) (10⁸/ Ml) was used to inoculate rice wilt bacteria-infected bacteria. Seed disinfectants were prepared according to Example 2 by diluting the wettable powders or control agents of various amino acid metal complex compounds shown in Table 3 with water to a predetermined concentration.
[0092]
To this chemical solution, the rice wilt bacterial pathogen-infected rice cake obtained by the above method was added so that the volume ratio (v / v) of the seed meal to the chemical solution was 1: 1, and the mixture was kept at 20 ° C. for 24 hours. The seed pods were soaked and disinfected for a long time. The seed pods after disinfection were immersed in water at 20 ° C. for 3 days, then drained and germinated at 30 ° C. for 24 hours. Then, the seed pods in the form of pigeon breasts were sown on Kumiai granular cultivated soil K (manufactured by Kureha Chemical Co., Ltd.) according to a conventional box raising method, and germinated at 32 ° C. for 2 days. Thereafter, the cultivation was managed in a glass greenhouse.
[0093]
The investigation of the presence or absence of disease was conducted 21 days after sowing (2.5 leaf stage) by investigating the number of seedlings and healthy seedlings of rice blight bacterial disease according to the following survey criteria (about 150 per box). In the same manner as above, the disease severity was determined, and the control value (%) was calculated and converted into an evaluation value. Further, as in Test Example 1, the degree of phytotoxicity to rice was also investigated.
The results are shown in Table 3.
Survey criteria for disease onset
N₀: Number of seedlings not affected
N₁: Leaf whitening due to disease is observed, but the number of seedlings is almost the same as healthy seedlings N₂: Number of seedlings whose leaf blades are whitened due to disease
N_Three: Withering
[0094]
[Table 3]

[0095]
[Test Example 3]
(Seed sterilization effect test for rice brown stripe control)
As the test rice cake, a concentrated bacterial suspension of rice (variety: Kirara 397) and a rice brown fungus (Pseudomonas avenae) (10⁸/ Ml) was used to infect rice brown stripe fungus-infected rice. Seed disinfectants were prepared according to Example 2 and prepared by diluting various amino acid metal complex compound wettable powders or control agents shown in Table 4 with water to a predetermined concentration.
[0096]
Into this chemical solution, the rice brown streak-infecting rice cake obtained by the above method was added so that the volume ratio (v / v) of the seed meal to the chemical solution was 1: 1, and the mixture was kept at 20 ° C. for 24 hours. The seed pods were immersed and disinfected. The seed pods after disinfection were immersed in water at 20 ° C. for 3 days, then drained and germinated at 30 ° C. for 24 hours. Then, the seed pods in the form of pigeon breasts were sown on Kumiai granular cultivated soil K (manufactured by Kureha Chemical Co., Ltd.) according to a conventional box raising method, and germinated at 32 ° C. for 2 days. Thereafter, the cultivation was managed in a glass greenhouse.
[0097]
To investigate the presence or absence of disease, the number of rice brown stripe disease seedlings and the number of healthy seedlings were examined 21 days after sowing (2.5 leaf stage) according to the following survey criteria (about 150 per box). Similarly, the disease severity was determined, and the control value (%) was calculated and converted into an evaluation value. Further, as in Test Example 1, the degree of phytotoxicity to rice was also investigated.
The results are shown in Table 4.
Survey criteria for disease onset
N₀: Number of seedlings not affected
N₁： Spots are found on imperfect leaves, but the number of seedlings is almost the same as healthy seedlings
N₂: Number of seedlings with lesions on leaf sheath and leaf blades and poor growth
N_Three: Withering
[0098]
[Table 4]

[0099]
[Test Example 4]
(Seed disinfection effect test for controlling rice seedling blight)
As a test meal, rice bran (variety: Kirara 397) was added in a bacterial suspension of Pseudomonas plantarii (10⁶cfu / ml) was inoculated under reduced pressure to obtain rice seedling blight disease-affected pods. Agricultural and horticultural fungicides containing commercially available copper hydroxide and basic copper chloride as one of the active ingredients were diluted to a predetermined concentration with water. An amino acid was added to the sterilizing agent diluted solution to a predetermined concentration to prepare a seed disinfecting solution.
[0100]
In the obtained seed disinfectant solution (medicine solution, soaking water), the seedlings of rice seedling blight disease obtained by the above-described method were added at 20 ° C. so that the volume ratio of the seed pod to the chemical solution was 1: 1. Soaked for 24 hours. Thereafter, the seed pods after immersion in the chemical solution were seeded at 20 ° C. for 3 days while changing the amount of the chemical solution (amount of seed water) so that the volume ratio of the seed pod to the seed water was 1: 2. The seed pods after soaking are drained, steamed for 24 hours at 30 ° C, and the seed pods that have become pigeon breasts are sown on a commercially available granular seedling culture soil (manufactured by Kureha Chemical Industry Co., Ltd.) according to the conventional seedling method. The budding process was performed at 32 ° C. for 2 days. After that, the disease was managed in a glass greenhouse.
[0101]
Hereinafter, in the same manner as in each of the above test examples, the phytotoxicity was evaluated and the control value was calculated.
The results are shown in Table 5.
[0102]
[Table 5]

[0103]
Figures in parentheses indicate the severity of the disease.
Wettable powder (3): Commercial preparation; Pephrazoate + fludioxonil + basic copper chloride wettable powder (pefrazoate 12% + fludioxonil 2% + basic copper chloride 7.6%, including 4.5% as copper)
Flowable (4): Commercial formulation; ipconazole + cupric hydroxide flowable flowable (contains 5% ipconazole + 4.6% cupric hydroxide, 3% copper)
Cupric hydroxide wettable powder (1): Commercially available preparation (containing cupric hydroxide as an active ingredient and 17% copper)
Basic copper chloride wettable powder (2): Commercially available formulation (basic chlorinating agent is used as active ingredient and contains 50% copper)
[0104]
[Test Example 5]
(Seed disinfection effect test for controlling rice seedling blight)
As a test meal, rice bran (variety: Kirara 397) was added in a bacterial suspension of Pseudomonas plantarii (10⁶cfu / ml) was inoculated under reduced pressure to obtain rice seedling blight disease-affected pods. Agricultural and horticultural fungicides containing commercially available copper hydroxide and basic copper chloride as one of the active ingredients were diluted to a predetermined concentration with water.
[0105]
In the obtained seed disinfectant solution (chemical solution, soaking water), the seedlings of rice seedling blight disease obtained by the above method are set so that the volume ratio of seed pods and seed disinfectant solution (chemical solution) is 1: 1. And soaked at 20 ° C. for 24 hours. Thereafter, the seed meal after immersion in the chemical solution was soaked in water at 20 ° C. for 3 days while changing the amount of the chemical solution so that the volume ratio of the seed meal to the immersion water was 1: 2.
In Test Example 5, L-lysine hydrochloride is used at a predetermined concentration (1) immediately before soaking the seed pod (immediately after adjustment of the seed disinfectant chemical solution), (2) immediately before sowing seed soaking (at the start of soaking after completion of chemical soaking) (3) Seeding water), (3) Amino acids were added after 2 days of soaking.
[0106]
The seed pods after soaking are drained, steamed for 24 hours at 30 ° C, and the seed pods that have become pigeon breasts are sown on a commercially available granular seedling culture soil (manufactured by Kureha Chemical Industry Co., Ltd.) according to the conventional seedling method. The budding process was performed at 32 ° C. for 2 days. After that, the disease was managed in a glass greenhouse.
Hereinafter, in the same manner as in each of the above test examples, the phytotoxicity was evaluated and the control value was calculated.
[0107]
The results are shown in Table 6.
[0108]
[Table 6]

[0109]
Figures in parentheses indicate the severity of the disease.
The wettable powder (3), flowable (4), cupric hydroxide wettable powder (1), and basic copper chloride wettable powder (2) are the same as described above.

Claims (4)

An agricultural and horticultural seed disinfectant comprising an amino acid metal complex compound represented by the following formula [I] or a salt thereof as an active ingredient;

[In the formula [I],
R ¹ and R ² may be the same as or different from each other. Asparagine side chain, aspartic acid side chain, alanine side chain, arginine side chain, isoleucine side chain, ornithine side chain, glycine side chain, glutamine side chain, glutamic acid side Chain, 2,4-diaminobutyric acid side chain, 2,3-diaminopropionic acid side chain, serine side chain, tryptophan side chain, 4-thiadiline side chain, threonine side chain, valine side chain, histidine side chain, hydroxyproline Indicates side chain, hydroxylysine side chain, proline side chain, phenylalanine side chain, lysine side chain or leucine side chain,
M represents copper. ] (i) asparagine, aspartic acid, alanine, arginine, isoleucine, ornithine, glycine, glutamine, glutamic acid, 2,4-diaminobutyric acid, 2,3-diaminopropionic acid, serine, tryptophan, 4-thiadiline, threonine, valine, Histidine, hydroxyproline, hydroxylysine, proline, phenylalanine, lysine or leucine or a salt thereof;
(ii) an inorganic copper compound;
A seed disinfectant for agricultural and horticultural use comprising the amino acid metal complex compound or salt thereof according to claim 1 obtained by blending as an active ingredient.   The agricultural and horticultural seed disinfectant according to claim 2, wherein the inorganic copper compound is at least one of copper suboxide, copper hydroxide, and copper salt.   An agricultural and horticultural fungicide containing an inorganic copper compound as an active ingredient, water, asparagine, aspartic acid, alanine, arginine, isoleucine, ornithine, glycine, glutamine, glutamic acid, 2,4-diaminobutyric acid, 2,3- It was obtained by blending diaminopropionic acid, serine, tryptophan, 4-thiadiline, threonine, valine, histidine, hydroxyproline, hydroxylysine, proline, phenylalanine, lysine or leucine or a salt thereof simultaneously or in any order. A seed disinfection method comprising disinfecting seeds using the amino acid metal complex compound or a salt thereof according to claim 1.