【発明の詳細な説明】[Detailed description of the invention]
本発明は土壌中に棲息して植物の地下部にある
根や塊茎に寄生してその正常な発育を阻害する種
種の植物寄生性線虫や細菌、糸状菌等の有害な土
壌微生物類の駆除に卓効を有し、しかも施用が容
易な作業性の優れた土壌施用殺線虫、殺微生物剤
を提供せんとするものであり、特に、メチルイソ
チオシアネート（以下MITCと称する）を有効成
分として含有する粉粒状の殺線虫、殺微生物剤に
関する。
MITCは化学式CH3NCS、融点35℃、沸点119
℃の極めて揮発性の高い低融点の固体であり、溶
剤に溶解して油剤又は乳剤の殺線虫剤及び土壌殺
菌剤として市販されているが、施用の際に特殊な
器具を用いて一定の間隔をおいて土壌中に点注し
なければならないため、使用法が面倒であり、ま
た、点注した個処を中心に濃度分布を生じ、その
ため均一且充分な効果が得難いと共に栽培作業に
薬害を生じ易い難点があつた。一方、従来より土
壌施用農薬の製剤形態の一種として活性成分を固
体担体に担持した粉、粒剤があり、これは上記の
如き液剤の点注と較べて施用が簡単で、薬剤を容
易に土壌中に混和することができるため、均一な
効果が期待され、土壌中の部分的な高濃度による
薬害が出難いという利点があることが知られてい
る。しかし、MITCの粉、粒剤化に於いては次の
ような問題点があり、その実用化は困難であると
言われていた。即ち、MITCは前述の如く極めて
揮発性が高いため、固体担体に安定に保持するこ
とが難しく仮え或る程度担持できても容器を開放
し土壌に散布すると土壌中に混和する前に直ちに
揮散してしまうため、散布と混和を素早く行わな
いと所定の有効量を施用し難いこと、しかも
MITCの蒸気は催涙性、皮膚刺激性を有するた
め、施用時のMITCの揮散は施用者に対して甚し
く有害であること……等々。尚、粉、粒剤化の技
術の上からは手段を選ばず強引に粉、粒剤化すれ
ば、MITCを担体と共に固化することは必ずしも
不可能ではないが、余り緊密に固化したのでは、
薬剤が土壌中に長期間残留し薬害を生じたり、或
いは薬剤の放出量が少な過ぎて効果が生じなかつ
たり、また、余り高価な材料を用いたり、製造工
程が複雑では経済性が悪く農薬としての実用性を
損うこととなる。
本発明者らはかくの如き現状に鑑み、MITCの
粉、粒状化に関し、先ずMITCの吸着性、保持性
が良く、比較的多量のMITCを吸蔵し、安定に保
持し得ること、吸蔵されたMITCは保管中や散布
時には揮散しないが、混和後の土壌中では放散さ
れ易いこと、好ましくは、一昼夜位でほぼ全量が
土壌中に拡散する程度のもの、更には、適当な流
動性を有すること、経済性、実用性が高いこと等
の観点から種種の担体について試験・研究を重ね
た結果、農薬製剤上一般に慣用されている担体物
質の殆んどは一長一短あり上記の目的には適当で
はなかつたが、例外的に有効細孔径が約3.5〜６
Åの天然又は合成フオージヤサイトが所期の目的
に適うものであることが認められ先に特許出願を
した。その後更に検討を重ねた結果、新たに有効
細孔径が約７Åの合成モルデナイトにも同様の機
能があることが認められ本発明を完成するに至つ
た。
即ち、本発明はMITCを有効細孔径が約７Åの
合成モルデナイトに担持してなる粉、粒状の固体
農薬組成物を提供せんとするものである。
以下、本発明について更に詳細に説明する。
モルデナイトは化学的には立体網状構造を有す
る結晶性のアルミノ・シリケートの含水アルカリ
金属塩又はアルカリ土類金属塩であり、天然品及
び合成品があり非常に多種のものが知られている
が、本発明者らは、これらの中で有効細孔径が約
７Åの合成モルデナイトが特異的に有効であるこ
とを見い出した。
合成モルデナイトを担体として用いる場合、製
品の粒度は必ずしも制限はなく、300メツシユ以
下の粉剤から10〜50メツシユの細粒剤、その他数
mm程度の成型品等種々の形状にて用いられるが、
通常は押出造粒法や転動造粒法、圧縮造粒法その
他の慣用の方法にて適当な大きさに造粒して用い
ることが好ましい。その際に粒子の機械的強度や
流動性の改善、或いは製造コストの低減等の観点
から、バインダーや滑剤、増量剤等として、ベン
トナイト、クレー、タルク、カオリン、炭酸カル
シウム、ケイソウ土等の物質を添加したり併用し
ても良い。尚、合成モルデナイトは一般に水を含
んでおり、そのままではMITCの安定した吸蔵力
が得られないため、担持する前に予め熱処理をし
て充分に脱水乾燥しておかなければならない。こ
の場合熱処理の温度及び時間としては100〜700
℃、好ましくは200〜500℃、１〜10時間程度で充
分である。
MITCの担持量については、必ずしも、厳密な
制限は無いが、少な過るときは粉、粒剤としての
散布量が多くなり、一方、多過るときはMITCの
吸蔵量に安定性が乏しくなるため、通常は合成モ
ルデナイト１部に対しMITC0.05〜0.5重量部、好
ましくは0.1〜0.4重量部程度が適当である。尚、
担体にMITCを担持させる方法としては、浸漬法
等一般に慣用されている方法のいずれでも良い
が、通常は担体にMITCを液状にて接触せしめ吸
着させる方法が好適である。この場合、MITCは
融点35℃であり、常温では固体であるため、通常
は加熱融解するか或いは適当な有機溶媒に溶解し
て用いると良い。この際使用すべき溶媒としては
MITCと反応したり分解したりしない安定なもの
で、MITCと相溶性の良いものであれば特に制限
はない。また、担持すべき活性成分としてMITC
以外に他の殺線虫剤や土壌殺菌剤等土壌中の有害
な微生物に対して生物学的に活性な化合物を併用
しても良く、特に、該化合物として揮発性が有
り、常温で液状且MITCと相溶性の有るものを用
いれば、上記溶媒をも兼ね極めて好都合である。
本発明の粒剤は有効成分としてMITCを含み、
更に必要に応じて他の土壌病害虫に活性な成分を
含むものであり、従つて、その施用法（対象、用
量）は本質的にはMITC（及び他の活性成分）の
それと異なるところはない。例えば、MITCを有
効成分として含有する。
本発明の粉粒剤は土壌中に棲息し、植物の根や
塊茎等の地下部に寄生する各種線虫類、例えばサ
ツマイモネコブセンチユウ、キタネコブセンチユ
ウ、アレナリアネコブセンチユウ、リンゴネコブ
センチユウ等のネコブセンチユウ、ダイズシスト
センチユウ、ムギシストセンチユウ、オカボシス
トセンチユウ、バレイシヨシストセンチユウ、ビ
ートシストセンチユウ等のシストセンチユウ、ミ
ナミネグサレセンチユウ、キタネグサレセンチユ
ウ、ムギネグサレセンチユウ、クルミネグサレセ
ンチユウ、チヤネグサレセンチユウ等のネグサレ
センチユウその他ワセンチユウ、サヤワセンチユ
ウ、ピンセンチユウ、ラセンセンチユウ、ミカン
ネセンチユウ、イシユクセンチユウ、ユミハリセ
ンチユウ等の外部寄生線虫や土壌中より植物体に
侵入し葉、花、茎等の地上部に寄生して被害を及
ぼすイチゴセンチユウ、ハガレセンチユウ等のハ
センチユウやクキセンチユウ等広範な線虫の駆動
に用いられる。施用量としては通常、有効成分量
として１〜30Kg／10a、好ましくは５〜15Kg／
10a程度が適当である。しかし、これは一応の目
安であり具体的には例えば、対象となる作物の種
類、線虫の種類、被害の程度、土壌条件、季節、
天候等により適宜加減して用いられる。
以下、本発明について代表的な例を示し更に詳
しく説明するが、これは本発明についての理解を
容易にするための単なる例示であり、従つて、本
発明はこれらによつて何ら制限されないことは言
うまでもない。
実施例 １
MITC2部（重量部、以下同じ）をキシレン１
部に溶解し、これに担体12部を加えて一昼夜密栓
放置して担持せしめた後、その１部を採り各試料
について２ｇ宛をガラスシヤーレ（95mmφ）にそ
れぞれ入れ、温度24℃、湿度70％の室内に放置し
た。一定時間後に、この粒剤を10％の水を含むア
セトン20mlにて振とう抽出し、シクロヘキサノン
を内部標準物質として用いてガスクロマトグラフ
イーにて分析した。尚、試料の抽出は１時間振と
う後１夜放置し、再び１時間振とうを繰返した。
試験に用いた多数の担体の中から代表的なもの
を選べば以下の通りである。
Ａ：ホワイトカーボン（ベントナイト30重量％を
加え、1.6mmφに押出し造粒後、100℃、１時間
乾燥）
Ｂ：ケイソウ土（Ａと同様に造粒、乾燥）
Ｃ：焼成ケイソウ土（Ａと同様に造粒、乾燥）
Ｄ：活性炭（市販0.5mmφ粒状品）
Ｅ：バーミキユライト（市販１〜２mmφ粒剤）
Ｆ：焼成カオリン（市販0.4〜１mmφ粒剤）
Ｇ：合成フオージヤサイト（市販品モレキユラー
シーブ3A、有効細孔径約2.5Å1.6mmφ粒剤）
Ｈ：合成フオージヤサイト（市販品モレキユラー
シーブ4A、有効細孔径約3.5Å1.6mmφ粒剤）
Ｉ：合成フオージヤサイト（市販品モレキユラー
シーブ5A、有効細孔径約4.2Å1.6mmφ粒剤）
Ｊ：合成フオージヤサイト（市販品モレキユラー
シーブ10X、有効細孔径約９Å1.6mmφ粒剤）
Ｋ：合成フオージヤサイト（市販品モレキユラー
シーブ13X、有効細孔径約10.0Å1.6mmφ粒剤）
Ｌ：合成モルデナイト（市販品ゼオロン900NA
有効細孔径約７Å1.6mmφ粒剤）
Ｍ：合成モルデナイト（市販品ゼオロン900H有
効細孔径約８〜９Å1.6mmφ粒剤）
Ｎ：合成モルデナイト（市販品ゼオロンAW−
300有効細孔径約４Å1.6mmφ粒剤）
結果を表−に示す。
この表からも明らかな如く、担体として(H)、(I)
〔特願昭57−125872〕及び(L)以外は担持された
MITCは開放状態では短時間のうちに揮散して残
存量が急激に減少する。また、同じ合成モルデナ
イトでも有効細孔径によつて顕著な差があること
が認められる。
実施例 ２
１／5000aのワグネルポツトにサツマイモネコ
ブセンチユウで汚染された畑地土壌を20cmの深さ
まで、その表面に実施例１の各種粒剤の中から代
表的なものを選びMITC4Kg／10aに相当する量散
布した。散布後一定時間放置してからポツトの土
壌と充分に混和し、ポツトの表面をビニールシー
トにて覆い、１週間放置した。１週間後ポツトの
土壌を充分に混和して１日放置してから、キウリ
の稚苗２本を定植し生育させた。３週間後に根を
取出し、形成された根コブ数によつて階級値を０
〜４の５段階に分け、次式によつて算出した根コ
ブ指数を求め、更に根コブ線虫防御率を求めた。
尚、試験は１供試粒剤につき３連にて行い、その
平均値を用いた。
根コブ指数＝〓（階級値）×個体数／全調査個体数×
４×100
根コブ線虫防御率＝100
−処理区根コブ指数／無処理を根コブ指数×100
結果を表に示す。
この表からも明らかな如く、(H)、(I)及び(L)以外
のものは散布後直ちに混和すれば所期の効果が得
られるが、散布と混和の時間差があると殆んど所
望の防除効果は得られない。これに対し、(H)、
(I)、(L)では散布後直ちに混和する必要はなく、比
較的長時間置いても良く、また、土壌中では活性
成分が充分拡散して所期の防除効果が発揮される
ことが認められる。
The present invention eliminates harmful soil microorganisms such as various plant-parasitic nematodes, bacteria, and filamentous fungi that live in the soil and parasitize the underground roots and tubers of plants, inhibiting their normal growth. The purpose of the present invention is to provide soil-applied nematicides and microbicides that are highly effective in the field, easy to apply, and have excellent workability. Contains powdery nematicides and microbicides. MITC has the chemical formula CH 3 NCS, melting point 35℃, boiling point 119
It is an extremely volatile, low-melting solid at 15°F (°C) and is commercially available as an oil or emulsion nematicide and soil fungicide after being dissolved in a solvent. It is cumbersome to use because it has to be injected into the soil at intervals, and the concentration distribution is centered around the individual injected areas, making it difficult to obtain a uniform and sufficient effect and causing chemical damage to cultivation operations. There was a problem that could easily cause problems. On the other hand, powders and granules, in which the active ingredient is supported on a solid carrier, have traditionally been a type of formulation for soil-applied pesticides. Because it can be mixed into the soil, it is expected to have a uniform effect, and it is known that it has the advantage of being less likely to cause chemical damage due to localized high concentrations in the soil. However, there are the following problems in making MITC into powders and granules, and it was said that it would be difficult to put it into practical use. In other words, as mentioned above, MITC is extremely volatile, so it is difficult to stably hold it on a solid carrier, and even if it can be held to a certain extent, when the container is opened and sprayed on the soil, it will immediately volatilize before being mixed into the soil. Therefore, it is difficult to apply the prescribed effective amount unless spraying and mixing are done quickly.
MITC vapor is lachrymatory and skin irritating, so the volatilization of MITC during application is extremely harmful to the user...etc. It should be noted that it is not necessarily impossible to solidify MITC together with the carrier if the powder or granule is forcibly made into powder or granule by any means possible from the standpoint of powder or granule technology, but if the MITC is solidified too tightly,
If the drug remains in the soil for a long time and causes chemical damage, or if the amount of the drug released is too small to be effective, or if too expensive materials are used or the manufacturing process is complicated, it may be uneconomical to use as a pesticide. This will impair the practicality of the system. In view of the current situation, the inventors of the present invention have focused on the powder and granulation of MITC, first of all, that it has good adsorption and retention properties for MITC, can occlude and stably retain a relatively large amount of MITC, and that Although MITC does not volatilize during storage or spraying, it should be easily dispersed in the soil after mixing, and preferably, it should be such that almost the entire amount is dispersed into the soil within a day or night, and it should also have appropriate fluidity. As a result of repeated tests and research on various types of carriers from the viewpoints of high economic efficiency and practicality, we found that most of the carrier materials commonly used in pesticide formulations have advantages and disadvantages and are not suitable for the above purposes. However, in exceptional cases, the effective pore diameter is approximately 3.5 to 6.
The natural or synthetic phosiasite of Å was found to be suitable for the intended purpose and a patent application was filed. As a result of further studies, it was discovered that a newly synthesized mordenite with an effective pore diameter of about 7 angstroms had a similar function, leading to the completion of the present invention. That is, the present invention provides a solid agricultural chemical composition in the form of powder or granules, in which MITC is supported on synthetic mordenite having an effective pore diameter of approximately 7 Å. The present invention will be explained in more detail below. Mordenite is chemically a hydrous alkali metal salt or alkaline earth metal salt of crystalline aluminosilicate with a three-dimensional network structure, and there are a wide variety of known products, including natural products and synthetic products. The present inventors have found that among these, synthetic mordenite with an effective pore diameter of about 7 Å is particularly effective. When synthetic mordenite is used as a carrier, the particle size of the product is not necessarily limited, and can range from powders of 300 mesh or less to fine granules of 10 to 50 mesh, and several others.
It is used in various shapes such as molded products of about mm size,
Usually, it is preferable to use extrusion granulation, rolling granulation, compression granulation, or other conventional methods to granulate the granules to an appropriate size. At this time, materials such as bentonite, clay, talc, kaolin, calcium carbonate, and diatomaceous earth are used as binders, lubricants, and fillers to improve the mechanical strength and fluidity of particles and to reduce manufacturing costs. It may be added or used in combination. Note that synthetic mordenite generally contains water and cannot provide a stable storage capacity for MITC if it is used as is, so it must be heat-treated and sufficiently dehydrated and dried before being supported. In this case, the heat treatment temperature and time are 100 to 700
℃, preferably 200 to 500℃ for about 1 to 10 hours is sufficient. There is not necessarily a strict limit on the amount of MITC supported, but if it is too small, the amount of powder or granules to be applied will increase, while if it is too large, the amount of MITC stored will be unstable. Therefore, it is usually appropriate to use MITC in an amount of about 0.05 to 0.5 parts by weight, preferably about 0.1 to 0.4 parts by weight, per part of synthetic mordenite. still,
As a method for supporting MITC on the carrier, any commonly used method such as a dipping method may be used, but it is usually preferable to contact the carrier with MITC in liquid form and adsorb it. In this case, since MITC has a melting point of 35° C. and is solid at room temperature, it is usually best to use it by melting it by heating or by dissolving it in a suitable organic solvent. The solvent that should be used at this time is
There are no particular restrictions as long as it is stable and does not react or decompose with MITC and has good compatibility with MITC. Additionally, MITC is used as the active ingredient to be supported.
In addition, compounds that are biologically active against harmful microorganisms in the soil, such as other nematicides and soil fungicides, may be used in combination.In particular, compounds that are volatile and liquid at room temperature. It is extremely convenient to use a solvent that is compatible with MITC and also serves as the above-mentioned solvent. The granules of the present invention contain MITC as an active ingredient,
Furthermore, it contains ingredients active against other soil pests as necessary, and therefore its application method (targets, dosage) is essentially no different from that of MITC (and other active ingredients). For example, it contains MITC as an active ingredient. The powder and granules of the present invention are suitable for various nematodes that live in the soil and parasitize underground parts such as roots and tubers of plants, such as sweet potato nematode, northern nematode, arenaria nematode, and apple nematode. Cyst centipedes such as Yuu, soybean cyst centipede, wheat cyst centipede, okabo cyst centipede, potato cyst centipede, beet cyst centipede, Minami Negusare centiyu, Northern Negusare centiyu, Mugine Other external parasitic lines such as Japanese centipede, walnut centipede, Chinese centipede, etc., and other external parasitic lines such as Japanese centipede, Japanese centipede, pincus centiyu, spiral centipede, Citrus centiflora, Ishiyuku centiyu, Yumihari centiyu, etc. It is used to drive a wide range of nematodes such as strawberry nematodes, peeling nematodes, and other nematodes that invade plants from the soil and parasitize above-ground parts such as leaves, flowers, and stems, causing damage. The application amount is usually 1 to 30 kg/10a, preferably 5 to 15 kg/10a as the amount of active ingredient.
Approximately 10a is appropriate. However, this is only a rough guideline, and specifically, for example, the type of target crop, type of nematode, degree of damage, soil conditions, season, etc.
It is used with appropriate adjustment depending on the weather etc. Hereinafter, typical examples of the present invention will be described in more detail, but these are merely illustrative examples to facilitate understanding of the present invention, and therefore, the present invention is not limited thereto in any way. Needless to say. Example 1 2 parts of MITC (parts by weight, the same applies hereinafter) to 1 part of xylene
After adding 12 parts of the carrier to this and allowing it to be supported overnight in a tightly sealed container, take 1 part of the solution and place 2 g of each sample in a glass shear dish (95 mmφ), and heat at 24°C and 70% humidity. I left it indoors. After a certain period of time, the granules were extracted by shaking with 20 ml of acetone containing 10% water, and analyzed by gas chromatography using cyclohexanone as an internal standard. The sample was extracted by shaking for 1 hour, left overnight, and shaking again for 1 hour. Representative carriers selected from among the many carriers used in the test are as follows. A: White carbon (added 30% by weight of bentonite, extruded to 1.6 mm diameter, dried at 100℃ for 1 hour) B: Diatomaceous earth (granulated and dried in the same way as A) C: Calcined diatomaceous earth (same as A) D: Activated carbon (commercially available 0.5mmφ granules) E: Vermiculite (commercially available 1-2mmφ granules) F: Calcined kaolin (commercially available 0.4-1mmφ granules) G: Synthetic phosiasite (commercially available granules) Molecular Sieve 3A, effective pore diameter approximately 2.5 Å 1.6 mmφ granules) H: Synthetic phosiasite (commercial product Molecular Sieve 4A, effective pore diameter approximately 3.5 Å 1.6 mm φ granules) I: Synthetic phagiasite ( Commercial product Molecular Sieve 5A, effective pore diameter approximately 4.2 Å 1.6 mmφ granules) J: Synthetic phosiasite (Commercial product Molecular Sieve 10X, effective pore diameter approximately 9 Å 1.6 mm φ granules) K: Synthetic phosiasite (Commercial product Molecular Sieve 13X, effective pore diameter approximately 10.0Å 1.6mmφ granules) L: Synthetic mordenite (Commercial product Zeolon 900NA
M: Synthetic mordenite (commercial product Zeolon 900H effective pore size approx. 8-9 Å 1.6 mmφ granules) N: Synthetic mordenite (commercial product Zeolon AW-
300 (effective pore diameter approximately 4 Å 1.6 mmφ granules) The results are shown in the table. As is clear from this table, (H) and (I) are used as carriers.
[Patent application 1987-125872] and except (L) were supported.
In an open state, MITC evaporates in a short time and the remaining amount decreases rapidly. Furthermore, it is recognized that even in the same synthetic mordenite, there are significant differences depending on the effective pore diameter. Example 2 Fill a 1/5000a Wagner pot with field soil contaminated with sweet potato nematode to a depth of 20 cm, and apply a representative one from the various granules of Example 1 to the surface of the soil to a depth of 20 cm, and apply a granule equivalent to MITC 4Kg/10a. amount was dispersed. After being sprayed, the mixture was allowed to stand for a certain period of time until it was thoroughly mixed with the soil in the pot, and the surface of the pot was covered with a vinyl sheet and left for one week. One week later, the soil in the pot was thoroughly mixed and left to stand for one day, after which two cucumber seedlings were planted and allowed to grow. After 3 weeks, the roots are taken out and the class value is set to 0 based on the number of root knots formed.
The root knot index was calculated using the following formula, and the root knot nematode protection rate was also determined.
The test was conducted three times for each granule sample, and the average value was used. Root Cobb index = 〓 (class value) × number of individuals / total number of surveyed individuals ×
4 x 100 Root kob nematode protection rate = 100 - Root kob index of treated section / Root kob index of untreated area x 100 The results are shown in the table. As is clear from this table, the desired effect can be obtained if the substances other than (H), (I) and (L) are mixed immediately after spraying, but if there is a time lag between spraying and mixing, the desired effect will not be achieved in most cases. No pest control effect can be obtained. On the other hand, (H),
For (I) and (L), it is not necessary to mix immediately after spraying, and it is possible to leave it for a relatively long time, and it has been found that the active ingredients are sufficiently diffused in the soil to exert the desired control effect. It will be done.
【表】【table】
【表】【table】
【表】【table】