JPS6241642B2

JPS6241642B2 -

Info

Publication number: JPS6241642B2
Application number: JP2381281A
Authority: JP
Inventors: Teruo Sugino
Original assignee: Yoshitomi Pharmaceutical Industries Ltd
Current assignee: Tanabe Pharma Corp
Priority date: 1981-02-19
Filing date: 1981-02-19
Publication date: 1987-09-03
Also published as: JPS57139004A

Description

[Detailed description of the invention]

本発明は海水中で木材を穿孔する生物の防除剤
に関する。より詳しくは、本発明は、一般式（式中、Ｒはヒドロキシ基を有していてもよい炭
素数６〜22の長鎖アルキル基を、R¹、R²、R³は
水素またはメチルを、ｎは２または３を示す。）
で表わされるアザラクタム化合物を有効成分とす
る木材穿孔性海産生物防除剤に関する。我国の木材需要は1979年で10900万m²であると
され、このうち約69％を輸入材に依存しているの
が現状である。外材が我国に輸入されると、陸上か、海中で貯
木されるが、この海中貯木においては、海中に生
息する木材穿孔生物、すなわち、フナクイムシ、
キクイムシ、キクイムシモドキ、コツブシムシな
どが貯木中の木材に付着、穿孔して大きな被害を
与える。これら海産生物は木造船の船底、木造桟
橋の橋脚などにも穿孔して生活している。木材資源の枯渇が危惧されている折、資源保護
のために、これらの木材穿孔生物による被害を食
い止めることは大きな意義がある。貯木場での虫害対策として、陸上では、陸上昆
虫類に対して有機燐剤のフエニトロチオン、マラ
チオン、ダイアジノン製剤が原木の表面に一定期
間毎に散布されている。しかし、海中では、これ
らの薬剤の使用は環境汚染の点から困難なので、
海中貯木では、何らの対策も取られていないのが
現状である。本発明者は、この様な現状に鑑み、木材穿孔性
海産生物防除剤について鋭意研究を重ねた結果、
殺菌剤としての用途は知られているが、木材穿孔
性海産生物に対しての効果は全く知られていない
前記アザラクタム化合物（）がフナクイムシ、
キクイムシなどに極めて有効であることを見出
し、本発明を完成したものである。本発明のアザラクタム化合物（）は極めて微
量でフナクイムシ幼性、キクイムシ幼生などの木
材付着防止効果を有し、その実用濃度は、通常、
海水中0.001〜50ppm程度が好ましく、貯木場の
海水中に所定濃度になる様に添加して木材を貯木
すればよい。この場合、本発明化合物を海水に均一に分散さ
せるために、適当な溶媒、たとえば水、灯油、キ
シレン、トルエン、エチレングリコール、シクロ
ヘキサノール、アセトン、メチルセロソルブ、ジ
オクチルフタレート、メチルエチルケトンに溶解
させ、必要に応じて界面活性剤を添加して製剤化
したものが好ましい。その際の界面活性剤として
は、高級脂肪酸塩類、特殊カルボン酸型高分子活
性剤、ポリオキシエチレンアルキルエーテル類、
ポリオキシエチレンソルビタンアルキルエステル
類、ソルビタンアルキルエステル類、ポリオキシ
エチレンノニルフエノールエーテル類、ポリオキ
シエチレン脂肪酸エステル類などがあげられる。
これ以外のペースト剤、ゼリー剤、水和剤などの
剤型としても用いることができる。さらに、遅効
性剤型として、加熱溶融した油脂に本発明化合物
と粉末状水溶性高分子化合物を熱時混和したのち
成型したものや、脂肪酸のアルカリ金属塩あるい
はアミン塩に本発明化合物を添加混合成型したも
のでもよい。本発明のアザラクタム化合物（）に、１・２
−ベンズイソチアゾリン−３−オン、塩化ベンゼ
トニウム、塩化ベンザルコニウム、（２−ピリジ
ルチオ−１−オキシド）ナトリウム、Ｎ・N′・
N″−トリスヒドロキシエチルヘキサハイドロ−
ｓ−トリアジンなどの化合物を併用すると、さら
に相剰的な効果を得ることもできる。次に、実施例、試験例により本発明を具体的に
説明する。例中“部”とは“重量部”である。実施例、試験例で用いた化合物は次の通りであ
る。実施例１本発明化合物60部、キシレン20部、ポリオキシ
エチレン脂肪酸モノエステル10部、ポリオキシエ
チレンアルキルエーテル10部を混合して乳剤を得
る。実施例２本発明化合物25部と塩化ベンゼトニウム25部と
の混合物に、ポリエチレンワツクス10部とポリエ
チレングリコール10部とを加え、適量のキシレン
に混合し、加熱溶解後、練合し、成形、乾燥す
る。実施例３本発明化合物40部、硅藻土35部、クレー20部、
ラウリルスルホン酸塩３部、カルボキシメチルセ
ルロース２部を粉砕混合して水和剤を得る。実施例４牛脂：ヤシ油＝１：１の混合物と苛性ソーダか
ら常法により得られた石鹸素地100部に、本発明
化合物：１・２−ベンズイソチアゾリン−３−オ
ン＝３：１を20部添加混合し、常法により石鹸や
作り、乾燥する。実施例５本発明化合物40部と塩化ベンゼトニウム20部と
をトルエン10部に加え、これをアスフアルトプラ
イマー（シエル石油(株)製）30部に加え、アスフア
ルト乳剤とする。試験例１化合物A50部をキシレン40部とエマルゲン903
（花王石鹸(株)製）10部で乳剤とし、海水で希釈し
て試験液とする。フナクイムシの飼育水槽内よりプランクトンネ
ツトで採取したフナクイムシ幼生をそのまま各濃
度の試験液中に10時間浸漬し、その後無処理の海
水中で48時間飼育した後、立体顕微鏡で生存幼生
数の有無をみた。海水温度22℃。結果を第１表に
示す。 The present invention relates to an agent for controlling organisms that bore into wood in seawater. More specifically, the present invention relates to the general formula (In the formula, R represents a long chain alkyl group with 6 to 22 carbon atoms which may have a hydroxy group, R ¹ , R ² and R ³ represent hydrogen or methyl, and n represents 2 or 3.)
This invention relates to a wood-boring marine organism control agent containing an azalactam compound represented by the following as an active ingredient. Japan's demand for wood in 1979 was estimated at 109 million ^m2 , of which approximately 69% is currently dependent on imported wood. When foreign timber is imported into Japan, it is stored either on land or in the sea, but in this underwater storage, wood-boring organisms that live in the sea, such as sea bream beetles,
Bark beetles, bark beetles, and small beetles attach themselves to and bore holes in stored wood, causing great damage. These marine creatures also live in holes in the bottoms of wooden ships and the piers of wooden piers. At a time when there are concerns about the depletion of wood resources, it is of great significance to stop the damage caused by these wood-boring organisms in order to conserve resources. To prevent insect damage in lumber yards, on land, organic phosphorus agents such as fenitrothion, malathion, and diazinon are sprayed on the surface of logs at regular intervals to protect against terrestrial insects. However, it is difficult to use these drugs underwater due to environmental pollution.
Currently, no countermeasures have been taken for underwater wood storage. In view of the current situation, the present inventor has conducted extensive research on wood-boring marine organism control agents, and has found that:
Although its use as a fungicide is known, its effect on wood-boring marine organisms is completely unknown.
They discovered that it is extremely effective against bark beetles, etc., and completed the present invention. The azalactam compound () of the present invention has the effect of preventing the adhesion of carp beetle larvae, bark beetle larvae, etc. to wood in extremely small amounts, and its practical concentration is usually
It is preferably about 0.001 to 50 ppm in seawater, and the lumber may be stored by adding it to seawater at a lumber yard to a predetermined concentration. In this case, in order to uniformly disperse the compound of the present invention in seawater, it is dissolved in a suitable solvent such as water, kerosene, xylene, toluene, ethylene glycol, cyclohexanol, acetone, methyl cellosolve, dioctyl phthalate, methyl ethyl ketone, and as necessary. Preferably, the formulation is prepared by adding a surfactant accordingly. The surfactants used in this case include higher fatty acid salts, special carboxylic acid type polymer surfactants, polyoxyethylene alkyl ethers,
Examples include polyoxyethylene sorbitan alkyl esters, sorbitan alkyl esters, polyoxyethylene nonylphenol ethers, and polyoxyethylene fatty acid esters.
It can also be used in other dosage forms such as pastes, jelly preparations, and wettable powders. Furthermore, as slow-acting formulations, the compound of the present invention and a powdered water-soluble polymer compound are mixed under heat in heated and melted fats and oils, and then molded, and the compound of the present invention is added and mixed with alkali metal salts or amine salts of fatty acids. It may also be molded. The azalactam compound () of the present invention has 1 and 2
-benzisothiazolin-3-one, benzethonium chloride, benzalkonium chloride, sodium (2-pyridylthio-1-oxide), N・N′・
N″-Trishydroxyethylhexahydro-
Further additive effects can be obtained by using a compound such as s-triazine in combination. Next, the present invention will be specifically explained using Examples and Test Examples. In the examples, "parts" means "parts by weight." The compounds used in Examples and Test Examples are as follows. Example 1 An emulsion is obtained by mixing 60 parts of the compound of the present invention, 20 parts of xylene, 10 parts of polyoxyethylene fatty acid monoester, and 10 parts of polyoxyethylene alkyl ether. Example 2 10 parts of polyethylene wax and 10 parts of polyethylene glycol were added to a mixture of 25 parts of the compound of the present invention and 25 parts of benzethonium chloride, mixed with an appropriate amount of xylene, dissolved by heating, kneaded, molded, and dried. do. Example 3 40 parts of the compound of the present invention, 35 parts of diatomaceous earth, 20 parts of clay,
Three parts of lauryl sulfonate and two parts of carboxymethyl cellulose are ground and mixed to obtain a wettable powder. Example 4 20 parts of the compound of the present invention: 1,2-benzisothiazolin-3-one = 3:1 was added to 100 parts of a soap base obtained by a conventional method from a mixture of beef tallow: coconut oil = 1:1 and caustic soda. Mix, make soap and dry in the usual manner. Example 5 40 parts of the compound of the present invention and 20 parts of benzethonium chloride are added to 10 parts of toluene, and this is added to 30 parts of asphalt primer (manufactured by Shell Oil Co., Ltd.) to prepare an asphalt emulsion. Test example 1 50 parts of compound A, 40 parts of xylene and Emulgen 903
Make an emulsion with 10 parts (manufactured by Kao Soap Co., Ltd.) and dilute with seawater to use as a test solution. Funaku beetle larvae collected using a plankton net from a funaku beetle rearing tank were immersed in test solutions of various concentrations for 10 hours, then reared in untreated seawater for 48 hours, and the number of surviving larvae was observed using a stereomicroscope. . Sea water temperature 22℃. The results are shown in Table 1.

【表】試験例２化合物C40部と塩化ベンゼトニウム20部とをト
ルエン10部に加え、これをアスフアルトプライマ
ー30部に加えてアスフアルト乳剤とし、海水で所
定濃度に希釈する。この希釈液に、ベイツガ試験
片（４×４×30cm、含水率15％）を15分間浸漬後
１日室温で乾燥する。この試験片を海面下１ｍ（海水温度25℃）に垂
下し、30日後のフナクイムシ幼生およびキクイム
シ幼生の木材表面への付着を立体顕微鏡下で測定
した。結果を第２表に示す。[Table] Test Example 2 Add 40 parts of Compound C and 20 parts of benzethonium chloride to 10 parts of toluene, add this to 30 parts of asphalt primer to make an asphalt emulsion, and dilute with seawater to a specified concentration. A hemlock test piece (4 x 4 x 30 cm, water content 15%) was immersed in this diluted solution for 15 minutes and then dried at room temperature for one day. This test piece was suspended 1 m below the sea surface (seawater temperature 25° C.), and the adhesion of crucian beetle larvae and bark beetle larvae to the wood surface after 30 days was measured under a stereomicroscope. The results are shown in Table 2.

【表】【table】

【表】試験例３フナクイムシ幼生付着期に、海中貯木場を15×
15ｍ（深さ２ｍ）に仕切り、実施例４で調製した
石鹸（有効成分：化合物Ａ）40Kgをこの海水中に
溶解させ（有効成分として15ppm）、直径45cm×
長さ５ｍの米マツ丸太（樹皮なし）５本を浸漬さ
せる。３ケ月後のフナクイムシ、キクイムシの付
着穿孔度合をＸ線写真で調べた。無処理区として
は同一地域の通常の貯木場での米マツ丸太材をみ
た。結果を第３表に示す。[Table] Test example 3 During the adhesion period of the sea cucumber beetle larvae, the underwater wood storage area was
Divided into 15 m (depth 2 m), 40 kg of soap (active ingredient: compound A) prepared in Example 4 was dissolved in this seawater (15 ppm as active ingredient), 45 cm in diameter x
Soak 5 rice pine logs (without bark) 5m long. After 3 months, the degree of adhesion and perforation by crucian carp beetles and bark beetles was examined using X-ray photographs. As for the untreated area, we looked at American pine logs from a normal lumber yard in the same area. The results are shown in Table 3.

【table】

Claims

[Claims] 1. General formula (In the formula, R represents a long chain alkyl group with 6 to 22 carbon atoms which may have a hydroxy group, R ¹ , R ² and R ³ represent hydrogen or methyl, and n represents 2 or 3.)
A wood-boring marine organism control agent containing an azalactam compound represented by the following as an active ingredient.