【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、新規な農園芸用殺菌剤組成物に関す
る。
〔発明の背景〕
最近、農薬の使用による土壌汚染や作動残留毒
性がいわゆる農薬公害として社会問題となつて以
来、とくに安全性の高い農薬の開発が望まれてい
る。また、殺菌剤については、種々の薬剤に対す
る耐性菌の発生がその効果を阻害する結果とな
り、その対策が切望されている。
本発明者らは、上記の点にかんがみ、古来、農
園芸用殺菌剤として重要な役割を果して来た石灰
ボルドーに着目し、特定の銅化合物の殺菌作用に
ついて研究の結果、これを酢酸と混合して用いる
ことにより、各種農園芸病害菌に対して極めて高
い相乗的防除効果が得られ、かつその適用に際し
てのPHを調節することによつてその効果の持続性
をコントロールし得ることを見出し、本発明を完
成した。
〔発明の構成〕
本発明は、水酸化第二銅、塩基性塩化銅、塩基
性炭酸銅および塩基性硫酸銅からなる群から選ば
れる少なくとも１種の銅化合物と、酢酸とを有効
成分として含有することを特徴とする農園芸用殺
菌剤組成物である。
上記銅化合物は、アルカリ性溶液中ではイオン
が解離し難く、酸性溶液中では解離し易いという
特性を有する。従つてこれを酢酸と混合したもの
は、銅イオンを解離し易く、従つて速効的相乗効
果による病害防除作用を発揮する。この混合組成
物は、主に種子消毒用殺菌剤として使用すること
ができ、又は地上散布用殺菌剤として、例えばイ
ネごま葉枯病、イネいもち病、イネ紋枯病、ミカ
ン黒点病、キユウリ斑点性殺菌病等の病害の防除
に有効に使用することができる。
さらにこの混合組成物は、土壌処理剤として、
例えばキユウリ苗立枯病、キユウリ疫柄、トマト
青枯病、ハクサイしり腐れ病等の土壌病害の防除
に有効に使用することもできる。
本発明組成物は、極めて顕著な殺菌力を示し、
単独使用による効果からは予測し得ない強力な病
害抑制作用を有するとともに、その適用時のPHを
調節することによりその効果の持続性を容易にコ
ントロールすることができる。従つて、本発明組
成物はその対象病害や施用形態、施用条件の汎用
性においてすぐれ、土壌処理用、種子消毒用、或
は地上散布用等各種用途に適した農園芸用殺菌剤
ならびに抗植物ウイルス剤として使用し得る。
さらに本発明組成物は、前記のようにその薬効
が大であるため、その使用量や使用濃度を少なく
することができるので、銅成分が存在するにもか
かわらず、これによる薬害は極めて僅少である。
また酢酸は無害の食品添加物であるので、薬害も
しくは毒性の極めて少ない殺菌剤が得られる。
本発明組成物は、農薬製剤の慣例に従い、不活
性な固体担体、および湿展剤、界面活性剤等を用
いて、水和剤、粉剤、粒剤等の任意の剤型にして
使用することができる。これらの不活性な担体と
して、例えばタルク、クレー、カオリン、ケイソ
ウ土、ホワイト・カーボン等をあげることができ
る。とくに、ホワイト・カーボンを適宜使用する
ことにより、粉体化あるいは固形化することがで
きる。湿展剤としては、例えばリグニンスルホン
酸ソーダ、アルキルベンゼンスルホン酸ソーダ、
ジナフチルメタンスルホン酸ソーダ、ラウリルア
ルコール硫酸ソーダ、ポリオキシエチレンアルキ
ルアリルエーテル等をあげることができる。ま
た、界面活性剤として、とくに食品添加物、例え
ばレシチン、シヨ糖脂肪酸エステル、ソルビタン
脂肪酸エステル、モノグリセライド、ポリプロピ
レングリコール脂肪酸エステル等を用いること
は、本発明組成物の無公害化に有用である。
本発明組成物中の有効成分の含有率は、粉剤、
粒剤で１〜10％水和剤で40〜80％、また、銅化合
物と酢酸の混合重量比は１：0.22〜４が好まし
い。
以下実施例により本発明組成物の組成例を示
す。なお実施例中、「部」は「重量部」を示す。
実施例 １
（水和剤）
塩基性炭酸銅40部、酢酸20部、ホワイトカーボ
ン20部、アルキルベンゼンスルホン酸ソーダ10
部、及び硅藻土10部をよく混合、粉砕して水和剤
とする。使用に際しては、水で所定濃度に稀釈し
て散布する。
実施例 ２
（粉剤）
塩基性硫酸銅３部、酢酸６部、及びクレー91部
をよく混合粉砕して粉剤とする。使用に際して
は、所定量をそのまま散布する。
実施例 ３
（粒剤）
塩基性塩化銅10部、酢酸10部、ベントナイト50
部、クレー28.5部、アルキルベンゼンスルホン酸
ソーダ１部、及びPVA0.5部を均一に混合粉砕し
て水適量を加えてねり合わせ、造粒機で造粒後、
乾燥、篩別して粒剤とする。使用に際しては、所
定量をそのまま散布する。
次に試験例により本発明組成物の各種植物病害
に対する防除効果を説明する。試験結果は後に第
１表として示す。
試験例 １
土壌処理によるキユウリ苗立枯病防除試験
キユウリ苗立枯病菌（Pellicularia
filamentosa）を培養したフスマ培地（重量％±
２／フスマ培地１）を重量で10倍量の土に混合し
て汚染土を作つた。この汚染土250mlに供試薬剤
の所定濃度稀釈液100mlを流し込み、これにあら
かじめ催芽したキユウリ苗（品種：四葉）を各区
25本ずつ移植して、10日後に移植苗の立枯状況を
測定した。
試験例 ２
土壌処理によるキユウリ疾病防除試験
あらかじめキユウリ疾病菌（Phytophthora
capsici）を培養したジヤガイモ寒天平板培地を
コルクボーラー（直径：５mm）で打ち抜いて接種
源とした。供試薬剤の所定濃度希釈液200mlに、
キユウリ苗（品種：相模半白、本葉２葉）をポツ
トごと浸漬し、上記接種源３片をキユウリ苗の地
際部に接種した。接種10日後にキユウリ本葉の萎
凋状況を測定した。
試験例 ３
土壌処理によるトマト青枯病防除試験
供試薬剤の所定濃度希釈液200mlに、各区５本
ずつのトマト苗をポツトごと浸漬したのち、ブイ
ヨン培地にあらかじめ培養したトマト青枯病菌
（Pseudomonas solanacearum）の一定量を、ト
マト苗の地際部に流し込み、10日後にトマト本葉
の萎凋状況を測定した。
試験例 ４
土壌処理によるハクサイしり腐れ病防除試験
ハクサイしり腐れ病菌（Pellicularia
filamentosa）を培養したフスマ培地（重量％±
２／フスマ培地１）を重量で10倍量の土に混合し
て汚染土を作つた。この汚染土250mlに供試薬剤
の所定濃度稀釈液100mlを流し込み、これにあら
かじめ催芽したハクサイ苗を各区25本ずつ移植し
た。移植２週間後にハクサイの地際部の腐敗状況
を測定した。
試験例 ５
地上散布によるイネごま葉枯病防除試験
本葉３葉期のはち植えイネ（品種：十石）に、
供試薬剤の所定濃度希釈液を散布して屋外に１時
間放置し、ついでこれに、イネごま葉枯病原菌の
胞子懸濁液を噴霧接種し、温室内に３日間保持し
たのち、その病斑数を測定した。
試験例 ６
地上散布によるイネいもち病防除試験
あらかじめ、直径６cmの合成樹脂製ポツトに植
えて温室内で育成した第４葉期のイネ（品種：十
石）に、供試薬剤の所定濃度希釈液の１ポツト当
り40mlをスプレーガンで散布した。散布薬液が乾
いたのち、別にモミガラ培地（粉末酵素、エキ
ス、可溶性デンプン、シヨ糖、モミガラを含む）
で培養したイネいもち病菌（Pyricularia
oryzae）の胞子を水で懸濁して、これを均一に
イネに噴霧接種し、温度27℃、湿度95％以上の恒
温恒湿槽中に保持した。接種４日後にイネ１葉当
りの発病斑数を測定した。
試験例 ７
地上散布によるイネ紋枯病防除試験
あらかじめ、ポツトに植えて温室内で育成した
第５葉期のイネ（品種：十石）に、供試薬剤を常
法に従つて散布し、ついで２時間後に、イネ紋枯
病菌（Pellicularia sasakii）の菌叢（直径８mm
に打ち抜いたもの）をイネの新稍間にそう入して
上記菌を接種した。基葉部をビニールシートで覆
い、温室内に７日間保持したのち、イネの発病総
病斑長を測定した。
試験例 ８
地上散布によるミカン黒点病害防除試験
温州ミカンの約３年生実生苗（６寸鉢に２〜４
本植）の新稍に、供試薬剤の所定濃度希釈液を２
鉢当り40mlずつ均一に噴霧散布した。ついで、ミ
カン黒点病原菌培養液に殺菌水を加え、150培顕
微鏡下１視野中約200個の柄胞子懸濁液を調製し、
これを上記被験植物に噴霧して接種した。これを
接種箱に入れたまま約３日間温室内に保持したの
ち、温室に移し、接種約２〜３週間後の新稍の全
葉について、病斑数０……無発病（０）、１〜50
(1)、51〜150(2)、151以上(3)に分けて測定し、次式
によつて発病度を算出した。
発病度＝１×n1＋２×n2＋３×n3／３×Ｎ×100（％
）
ただし、n1、n2、n3はそれぞれ発病程度(1)、
(2)、(3)の葉数、Ｎは総葉数を示す。
試験例 ９
地上散布によるキユウリ斑点性細菌病防除試験
直径6.5cmの穴あきコツプにクレハソイルを詰
め、これに芽出しをしたキユウリ種子を１個ずつ
播種し、約２週間空調温室内で栽培した。ついで
これに試供薬剤の所定濃度希釈液をスプレーガン
で噴霧散布した。別に接種１週間後の罹病キユウ
リ葉１ｇ（生重）に少量の１／10M（PH7.0）リン
酸緩衝液を加えて磨砕し、ガーゼで濾過後さらに
前記のリン酸緩衝液を加えて100mlとし、これに
500メツシユカーボランダム100ｇを混合して接種
液とした。前記の散布薬剤を風乾させたキユウリ
株に、接種液をかくはんしながらスプレーガンで
吹付接種した。接種したキユウリ株はフアンジト
ロン内で生育させ、５〜７日後に発病株数を測定
した。
〔試験結果〕
試験例１〜９における測定値（計算値）は、い
ずれも次式を用いて各病害の防除価（％）として
算出し、その結果を第１表にまとめて示した。
防除価（％）＝１処理区の測定値（計算値）／無処理
区の測定値（計算値）
また本表中、薬害程度の欄は、薬害の全くない
ものを「−」、わずかにあるものを「±」、少しあ
るものを「＋」、かなりあるものを「＋＋」、はな
はだしいものを「＋＋＋」と表記した。
【表】DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel fungicide composition for agricultural and horticultural use. [Background of the Invention] Recently, since soil contamination and residual toxicity due to the use of agricultural chemicals have become social problems as so-called agricultural chemical pollution, there has been a desire to develop particularly safe agricultural chemicals. Furthermore, with regard to disinfectants, the development of resistant bacteria to various drugs has resulted in inhibiting their effectiveness, and countermeasures are desperately needed. In view of the above points, the present inventors focused on lime Bordeaux, which has played an important role as a fungicide for agriculture and horticulture since ancient times, and as a result of research on the bactericidal effect of a specific copper compound, mixed it with acetic acid. We have discovered that an extremely high synergistic control effect can be obtained against various agricultural and horticultural pathogens by using it as a compound, and that the sustainability of the effect can be controlled by adjusting the pH during application. The invention has been completed. [Structure of the Invention] The present invention contains at least one copper compound selected from the group consisting of cupric hydroxide, basic copper chloride, basic copper carbonate, and basic copper sulfate, and acetic acid as active ingredients. This is a fungicide composition for agricultural and horticultural use. The above-mentioned copper compound has a characteristic that ions are difficult to dissociate in an alkaline solution, and easily dissociated in an acidic solution. Therefore, when mixed with acetic acid, copper ions are easily dissociated, and therefore, a rapid synergistic disease control effect is exerted. This mixed composition can be used primarily as a fungicide for seed disinfection, or as a fungicide for ground spraying, such as rice sesame leaf blight, rice blast, rice sheath blight, citrus black spot, and cucumber spot. It can be effectively used to control diseases such as fungicidal diseases. Furthermore, this mixed composition can be used as a soil treatment agent.
For example, it can be effectively used to control soil diseases such as cucumber seedling damping-off, cucumber late blight, tomato bacterial wilt, and Chinese cabbage rot. The composition of the present invention exhibits extremely significant bactericidal activity,
It has a powerful disease-suppressing effect that cannot be predicted from the effects of single use, and the sustainability of its effect can be easily controlled by adjusting the pH at the time of application. Therefore, the composition of the present invention is excellent in its target diseases, application form, and versatility in application conditions, and is suitable as an agricultural and horticultural fungicide and anti-plant agent for various uses such as soil treatment, seed disinfection, and ground spraying. Can be used as a viral agent. Furthermore, since the composition of the present invention has high medicinal efficacy as described above, the amount and concentration used can be reduced, so that despite the presence of the copper component, the chemical damage caused by this is extremely small. be.
Furthermore, since acetic acid is a harmless food additive, a bactericide with extremely low phytotoxicity or toxicity can be obtained. The composition of the present invention can be used in any dosage form such as a wettable powder, powder, or granule using an inert solid carrier, a wetting agent, a surfactant, etc., in accordance with the customary practice of agrochemical formulations. Can be done. Examples of these inert carriers include talc, clay, kaolin, diatomaceous earth, and white carbon. In particular, by appropriately using white carbon, it can be pulverized or solidified. Examples of wetting agents include sodium ligninsulfonate, sodium alkylbenzenesulfonate,
Examples include sodium dinaphthyl methanesulfonate, sodium lauryl alcohol sulfate, and polyoxyethylene alkyl allyl ether. Furthermore, the use of food additives such as lecithin, sucrose fatty acid ester, sorbitan fatty acid ester, monoglyceride, polypropylene glycol fatty acid ester, etc. as a surfactant is useful for making the composition of the present invention pollution-free. The content of the active ingredient in the composition of the present invention is powder,
It is preferably 1 to 10% for granules and 40 to 80% for hydrating agents, and the mixing weight ratio of copper compound and acetic acid is preferably 1:0.22 to 4. Examples of compositions of the compositions of the present invention are shown below in Examples. In the examples, "parts" indicate "parts by weight." Example 1 (Wetting agent) 40 parts of basic copper carbonate, 20 parts of acetic acid, 20 parts of white carbon, 10 parts of sodium alkylbenzenesulfonate
1 part and 10 parts of diatomaceous earth are thoroughly mixed and ground to make a wettable powder. When using, dilute with water to a specified concentration and spray. Example 2 (Powder) 3 parts of basic copper sulfate, 6 parts of acetic acid, and 91 parts of clay are thoroughly mixed and ground to obtain a powder. When using, just spray the prescribed amount. Example 3 (granules) Basic copper chloride 10 parts, acetic acid 10 parts, bentonite 50 parts
1 part, 28.5 parts of clay, 1 part of sodium alkylbenzenesulfonate, and 0.5 part of PVA are uniformly mixed and pulverized, mixed with an appropriate amount of water, and granulated using a granulator.
Dry and sieve to make granules. When using, just spray the prescribed amount. Next, the control effects of the composition of the present invention on various plant diseases will be explained using test examples. The test results are shown later in Table 1. Test Example 1 Test for controlling cucumber seedling blight by soil treatment
filamentosa) cultured on bran medium (wt% ±
Contaminated soil was prepared by mixing 2/Bran medium 1) with 10 times the amount of soil by weight. Pour 100 ml of a diluted solution of the test chemical into 250 ml of this contaminated soil, and add pre-germinated cucumber seedlings (variety: four-leaf) to each area.
Twenty-five plants were transplanted at a time, and 10 days later, the condition of the transplanted seedlings was measured for withering. Test Example 2 Test for controlling cucumber diseases by soil treatment.
The inoculum was prepared by punching out a potato agar plate cultured with a cork borer (diameter: 5 mm). Add 200 ml of diluted solution of the test drug to the specified concentration.
A cucumber seedling (variety: Sagami Hanshiro, 2 true leaves) was soaked in a pot, and three pieces of the above-mentioned inoculum were inoculated at the ground level of the cucumber seedling. Ten days after inoculation, the wilting status of cucumber true leaves was measured. Test Example 3 Tomato bacterial wilt control test by soil treatment Five tomato seedlings in each pot were immersed in 200 ml of a predetermined concentration dilution of the test chemical, and then the tomato bacterial wilt fungus (Pseudomonas solanacearum, which had been cultured in advance in a bouillon medium) was immersed in a pot of 5 tomato seedlings in each group. ) was poured into the ground of tomato seedlings, and the wilting status of tomato true leaves was measured 10 days later. Test Example 4 Chinese cabbage end rot control test by soil treatment Chinese cabbage end rot disease fungus (Pellicularia
filamentosa) cultured on bran medium (wt% ±
Contaminated soil was prepared by mixing 2/Bran medium 1) with 10 times the amount of soil by weight. 100 ml of a diluted solution of the test chemical at a predetermined concentration was poured into 250 ml of this contaminated soil, and 25 pre-germinated Chinese cabbage seedlings were transplanted into each area. Two weeks after transplantation, the state of rot in the underground part of the Chinese cabbage was measured. Test example 5 Rice sesame leaf blight control test by ground spraying.
A diluted solution of a specified concentration of the test drug was sprayed and left outdoors for 1 hour, then a spore suspension of the rice sesame leaf blight pathogen was sprayed and inoculated, and after being kept in a greenhouse for 3 days, the lesions were removed. The number was measured. Test Example 6 Rice blast control test by ground spraying A diluted solution of the test chemical at a predetermined concentration was applied to fourth-leaf stage rice (variety: Jukoku) that had been planted in synthetic resin pots with a diameter of 6 cm and grown in a greenhouse in advance. 40ml per pot was sprayed with a spray gun. After the sprayed chemical solution has dried, separate rice hull culture medium (contains powdered enzyme, extract, soluble starch, sucrose, rice hull)
Rice blast fungus (Pyricularia
Oryzae) spores were suspended in water, uniformly sprayed and inoculated onto rice plants, and kept in a constant temperature and humidity chamber at a temperature of 27°C and a humidity of 95% or higher. Four days after inoculation, the number of diseased spots per rice leaf was measured. Test Example 7 Rice sheath blight control test by ground spraying The test chemicals were first sprayed in a conventional manner on rice (cultivar: Jukoku) at the 5th leaf stage, which had been planted in pots and grown in a greenhouse. After 2 hours, a bacterial colony of rice sheath blight (Pellicularia sasakii) (diameter 8 mm)
(cut out) into the new shoots of rice and inoculated with the above bacteria. The basal leaf part was covered with a vinyl sheet and kept in a greenhouse for 7 days, after which the total length of diseased lesions on the rice plants was measured. Test example 8 Orange black spot disease control test by ground spraying Approximately 3 year old unshiu orange seedlings (2 to 4 seedlings per 6 inch pot)
A diluted solution of the test drug at a specified concentration was applied to the new growth of the main plant.
A uniform spray of 40 ml per pot was applied. Next, sterilized water was added to the tangerine blackspot pathogen culture solution to prepare a suspension of about 200 stalk spores in one field of view under a 150-culture microscope.
This was sprayed and inoculated onto the above test plants. After keeping it in the greenhouse for about 3 days in the inoculation box, it was moved to the greenhouse, and about 2 to 3 weeks after inoculation, the number of lesions on all the new leaves was 0...no disease (0), 1 ~50
(1), 51 to 150 (2), and 151 or more (3), and the disease severity was calculated using the following formula. Disease severity = 1 x n 1 + 2 x n 2 + 3 x n 3 /3 x N x 100 (%
) However, n 1 , n 2 , and n 3 are the degree of onset (1), respectively.
The number of leaves in (2) and (3), N indicates the total number of leaves. Test Example 9 Test for controlling bacterial spot bacterial disease of cucumber by ground spraying A hole pot with a diameter of 6.5 cm was filled with Kureha soil, and one germinated cucumber seed was sown therein and cultivated in an air-conditioned greenhouse for about two weeks. Then, a diluted solution of a sample drug at a predetermined concentration was sprayed onto the sample using a spray gun. Separately, add a small amount of 1/10M (PH7.0) phosphate buffer to 1 g (fresh weight) of infected cucumber leaves one week after inoculation, grind, filter through gauze, and then add the above phosphate buffer. Make it 100ml and use this
500 mesh carborundum and 100 g were mixed to prepare an inoculation solution. The air-dried cucumber plant was inoculated with the above-mentioned spraying agent by spraying it with a spray gun while stirring the inoculum solution. The inoculated cucumber strains were grown in a fanzitron, and the number of diseased strains was measured 5 to 7 days later. [Test Results] The measured values (calculated values) in Test Examples 1 to 9 were all calculated as the control value (%) of each disease using the following formula, and the results are summarized in Table 1. Control value (%) = Measured value (calculated value) for 1 treatment area / Measured value (calculated value) for untreated area In addition, in this table, in the column for degree of chemical damage, "-" indicates no chemical damage, and "-" indicates that there is no chemical damage at all. A certain amount is written as ``±'', a little amount is written as ``+'', a considerable amount is written as ``++'', and a very large amount is written as ``+++''. 【table】