【０００１】[0001]
【産業上の利用分野】本発明は船舶、橋梁などの表面に
水棲汚損生物が付着するのを防止する方法に関する。本
明細書において水棲汚染生物とは、水中で人工構造物に
付着し、産業上、経済上の不利益をもたらす付着生物で
あって、個体が目視観察できる大きさに成長する大型付
着生物を言い、例えば、フジツボ、イガイ、カキ、ヒド
ロ虫、コケ虫、ホヤ、セルプラなどの動物、アオサ、シ
オミドロなどの植物を言う。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing aquatic fouling organisms from adhering to the surface of ships, bridges and the like. As used herein, aquatic contaminant organisms are attached organisms that attach to artificial structures in water and cause industrial and economic disadvantages, and refer to large attached organisms that grow to a size that can be visually observed by individuals. For example, animals such as barnacles, mussels, oysters, hydroids, bryophytes, ascidians, serplas, and the like, plants such as Ulva, Shioido, and the like.
【０００２】[0002]
【従来技術】船舶などの船底にフジツボ、セルプラ、ホ
ヤ、コチ虫、カキなど水棲生物が付着すると、重量増
加、水流抵抗の増加、巡航速度の低下などの問題を生
じ、船舶寿命の低下、燃料使用量の増加などの産業上の
問題を引き起こす。これらの水棲生物の付着を防止する
方法は古くから検討されており、付着を引き起こす生物
の天敵などを用いた生物学的方法、付着しがたい構造材
料の使用(例えば銅合金の使用、シリコーン系塗料、弗
素系塗料などの塗装)、幼虫の流入防止(例えば、スクリ
ーンで遮蔽する方法)、幼虫の駆除(例えば、光、紫外
線、色、超音波などの使用、昇温、酸欠など生存困難な
環境)、付着生物の機械的除去(例えば、洗浄、ジェット
洗浄、ブラッシング、吸引など)、化学的または生物化
学的方法(例えば、殺貝、忌避、防汚剤などの使用)など
が検討されている。最近では適用領域が広く、高い効果
が得られ、処理が容易であるなどの理由から、殺貝剤、
忌避剤、防汚剤などを含む船底塗料を塗布する方法が広
く採用され、また研究されてきた。しかしながら、これ
らの化学薬物を含む塗料は塗膜中の薬剤が徐々に水中に
溶出するか、あるいはこれを含む塗料が徐々に削られて
水中に散逸し、常に新しい塗装面が露出するように設計
されているので、海洋環境上悪影響を及ぼす懸念が指摘
されている。特に、１９８０年代に入って防汚剤として
最も代表的な錫化合物による魚貝類への汚染が指摘され
るや、ヨーロッパ各国および米国で錫含有船底塗料に様
々な規制が加えられ、これに代わる水棲生物による汚染
防止方法の開発が火急の課題として浮上している。しか
しながら、現在のところ、防汚剤などを含む防汚船底塗
料に代わる有力な方法は開発されていない。研究の方向
はもっぱら、錫化合物に代わる低毒性の防汚剤の開発に
向けられている。2. Description of the Related Art When aquatic organisms such as barnacles, cerpra, ascidians, kochi bugs and oysters adhere to the bottom of ships, they cause problems such as increased weight, increased water flow resistance, and reduced cruising speed, which reduce ship life and fuel consumption. It causes industrial problems such as increased usage. Methods for preventing adhesion of these aquatic organisms have been studied for a long time, and biological methods using natural enemies of organisms causing adhesion, use of structural materials that are difficult to attach (e.g. use of copper alloys, silicone-based materials) Paint, fluorine-based paint, etc., prevention of larva influx (for example, a method of shielding with a screen), larva extermination (for example, use of light, ultraviolet rays, color, ultrasonic waves, etc. Environment), mechanical removal of attached organisms (e.g. cleaning, jet cleaning, brushing, suction, etc.), chemical or biochemical methods (e.g. shellfish killing, repelling, use of antifouling agents, etc.), etc. ing. Recently, because of its wide range of application, high efficacy and easy treatment, shellfish killers,
A method of applying a ship bottom paint containing a repellent, an antifouling agent, etc. has been widely adopted and studied. However, paints containing these chemicals are designed so that the drug in the coating film gradually elutes in water, or the paint containing them gradually scrapes and dissipates in the water, and new paint surfaces are always exposed. Therefore, it has been pointed out that there is a concern that it will have an adverse effect on the marine environment. In particular, when it was pointed out that the tin compounds, which are the most representative antifouling agents in the 1980s, were contaminated by fish and shellfish, various regulations were added to tin-containing ship bottom paints in European countries and the United States, and they replaced the aquatic organisms. The development of a method for preventing biological pollution has emerged as an urgent issue. However, at present, no promising alternative to antifouling ship bottom paints containing antifouling agents has been developed. The focus of the research is on the development of low toxicity antifouling agents that replace tin compounds.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、防汚剤を用
いない大型水棲汚損生物の付着を阻止する付着防止剤を
提供することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide an antifouling agent which does not use an antifouling agent and which prevents the adhesion of large-scale aquatic fouling organisms.
【０００４】[0004]
【課題を解決するための手段】本発明は水中の構造体表
面にバイオゼリー層を形成させて、大型水棲汚損生物の
付着を防止するためのバイオゼリー形成剤に関する。The present invention relates to a biojelly forming agent for forming a biojelly layer on the surface of a structure in water to prevent the attachment of large aquatic fouling organisms.
【０００５】本発明において構造体とは船底、漁網、導
水管、橋梁などを言う。従来、水中構造体にはスライム
が付着していた。In the present invention, the structure means a ship bottom, a fishing net, a water conduit, a bridge and the like. Conventionally, slime was attached to the underwater structure.
【０００６】スライム層とは主として水中の生物の代謝
産物によって形成されるぬめり感のある薄膜層を言う。
従来、薄膜のスライム層は船底の汚染物質の一種として
除去する方向で検討されている。従ってこれを積極的に
フジツボ、アオサ、カキ、セルブラ、イガイなどの船舶
の寿命や運行に実質的に影響を与える大型の水棲汚損生
物の付着防止に利用する着想は存在しなかった。本発明
はこのスライム層を積極的に水中構造体の表面に形成さ
せ、これによって水棲汚損生物の付着を防止するバイオ
ゼリー形成剤に関するものであり、このような方法で水
棲汚損生物の付着を防止する方法は従来全く知られてい
ない。この様な目的に用いるスライム層としてはゼリー
状の厚さ０.３mm以上、より好ましくは０.５mmから６m
m、特に１mmから５mm程度のものが適している。従って
本発明では厚さ約０.３mm以上のスライム層を特にバイ
オゼリーと呼ぶ。本発明においてスライム層の厚さは試
験板を平面にし、室温で１時間放置後の膜厚をスケール
で測定した。このスライム層またはバイオゼリー層は前
述のごとく主として水中の生物、特に微生物の代謝産物
であるが、その中にバクテリア、ケイソウなどの生物が
棲息できる層であり、実際にそれらの生物が観察され
る。化学的には、各種の糖類、多糖類、脂質、糖蛋白、
リン脂質などが含まれている。ゼリー状の厚さ０.３mm
以上のスライム層は大型の水棲汚損生物の付着防止に特
に有用である。[0006] The slime layer is a slimy thin film layer formed mainly by metabolites of organisms in water.
Conventionally, thin slime layers have been studied as a type of contaminants on the bottom of ships. Therefore, there was no idea to positively use this to prevent the attachment of large-scale aquatic fouling organisms that substantially affect the lifespan and operation of ships such as barnacles, sea lions, oysters, cellulas and mussels. The present invention relates to a biojelly forming agent that positively forms this slime layer on the surface of an underwater structure, thereby preventing the attachment of aquatic fouling organisms, and prevents the attachment of aquatic fouling organisms by such a method. There is no known method to do so. The slime layer used for such a purpose has a jelly-like thickness of 0.3 mm or more, more preferably 0.5 mm to 6 m.
m, especially about 1 mm to 5 mm is suitable. Therefore, in the present invention, a slime layer having a thickness of about 0.3 mm or more is particularly called bio jelly. In the present invention, the thickness of the slime layer was determined by measuring the film thickness after allowing the test plate to be flat and leaving it at room temperature for 1 hour. As mentioned above, this slime layer or biojelly layer is mainly a metabolite of aquatic organisms, especially microorganisms, but it is a layer where organisms such as bacteria and diatoms can live, and those organisms are actually observed. . Chemically, various sugars, polysaccharides, lipids, glycoproteins,
Contains phospholipids, etc. Jelly-like thickness 0.3mm
The slime layer described above is particularly useful for preventing attachment of large-scale aquatic fouling organisms.
【０００７】スライム層はある種の化合物を含む塗料を
塗装することによって水中構造体上で積極的に形成させ
ることができる。これらの化合物を使用すると水中の構
造体表面に容易に厚みのあるスライム層、即ちバイオゼ
リーを形成することができ、従って、本明細書ではこの
ような性質を有する化合物を特にバイオゼリー形成剤と
言う。本発明は、スチリル基やシンナミル基のごとき芳
香族に直結した炭素がエチレン系不飽和結合を有する化
合物が厚みのあるスライム層を形成する性質のあること
を究明した点に特徴がある。即ち、本発明はスチリル基
またはシンナミル基を有する化合物を含有するバイオゼ
リー形成剤に関する。The slime layer can be positively formed on the underwater structure by applying a paint containing a certain compound. When these compounds are used, it is possible to easily form a thick slime layer, that is, biojelly, on the surface of a structure in water. Therefore, in the present specification, a compound having such properties is particularly referred to as a biojelly forming agent. To tell. The present invention is characterized in that it has been clarified that a compound having an ethylenically unsaturated bond in which carbon directly bonded to an aromatic such as a styryl group or a cinnamyl group has a property of forming a thick slime layer. That is, the present invention relates to a biojelly forming agent containing a compound having a styryl group or a cinnamyl group.
【０００８】本発明に有用なバイオゼリー形成剤の例を
下記一般式で示す。一般式：Examples of biojelly forming agents useful in the present invention are shown by the following general formula. General formula:
【化２】本発明に用いられる上記一般式で表される化合物は、代
表的にはＸが水素であるスチレン系化合物と、Ｘがカル
ボキシル基(桂皮酸系)、ヒドロキシメチル基(桂皮アル
コール系)、アルデヒド基(桂皮アルデヒド)、アミド(桂
皮アミド)等のシンナミル系化合とに大別できる。芳香
族基または芳香族基に直結する炭素は置換基を有してい
てもよい。芳香族基にはジビニルベンゼンのごとく、別
のエチレン系不飽和基、例えばビニル基(ｍ＝１のとき)
を有していてもよい。また別の置換基(Ｙ)、例えば前述
のごとき基を有していてもよい。置換基(Ｙ)はｎが０の
ときは、置換基のない状態、即ち、水素原子を示す。置
換基(Ｙ)の数は２以下が好ましい。Ｙがハロゲン原子の
ときは、Ｆ、Ｃｌ、Ｂｒ、Ｉいずれでもよいが、Ｃｌま
たはＢｒが好ましい。Ｙがアルキル基のときは分岐を有
してもよい飽和または不飽和のアルキル基、シクロアル
キル基、アラルキル基など、炭素数１〜１８、好ましく
は１〜１２、より好ましくは１〜１０である。炭素数お
よび置換基の数が多すぎると、スチリルまたはシンナミ
ル基あたりの分子量(単に当量と言う)が大きくなりすぎ
るため、好ましくない。アルキル基は、ハロゲンで置換
されていてもよい。その他の好ましいＹの例はアルコキ
シシリル基などがある。アルコキシシリル基は炭素数１
〜２のアルコキシ基が特に好ましい。アルコキシシリル
基はアルコキシシリルアルキル基であってもよい。この
場合のアルキル基は炭素数１〜２が好ましい。置換基
(Ｙ)はそれ自体反応性の基、例えば水酸基、アミノ基な
どであってもよい。Ｙがアルキル基の場合のアルキル基
の長さは、バイオゼリー形成剤成分の親和性や親油性を
調節し、塗料への相溶性を調節したり、塗料から水中へ
の移行性や徐放性を調節する上で有用である。[Chemical 2] The compound represented by the above general formula used in the present invention is typically a styrene compound in which X is hydrogen, X is a carboxyl group (cinnamic acid type), a hydroxymethyl group (cinnamic alcohol type), an aldehyde group. (Cinnamic aldehyde) and amide (cinnamic amide). The aromatic group or carbon directly connected to the aromatic group may have a substituent. As an aromatic group, another ethylenically unsaturated group such as divinylbenzene, eg vinyl group (when m = 1)
May have. Further, it may have another substituent (Y), for example, the groups described above. When n is 0, the substituent (Y) represents a state without a substituent, that is, a hydrogen atom. The number of substituents (Y) is preferably 2 or less. When Y is a halogen atom, it may be any of F, Cl, Br and I, but Cl or Br is preferred. When Y is an alkyl group, it has 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, such as a saturated or unsaturated alkyl group which may have a branch, a cycloalkyl group and an aralkyl group. . When the number of carbon atoms and the number of substituents are too large, the molecular weight per styryl or cinnamyl group (simply referred to as equivalent) becomes too large, which is not preferable. The alkyl group may be substituted with halogen. Examples of other preferred Yis andA Rukoki <br/> Shishiriru group. Alkoxysilyl group has 1 carbon
Alkoxy groups of ~ 2 are particularly preferred. The alkoxysilyl group may be an alkoxysilylalkyl group. In this case, the alkyl group preferably has 1 to 2 carbon atoms. Substituent
(Y) may itself be a reactive group such as a hydroxyl group or an amino group. When Y is an alkyl group, the length of the alkyl group adjusts the affinity and lipophilicity of the biojelly-forming agent component, adjusts the compatibility with the paint, and transfers from the paint to water and the sustained release property. Is useful in adjusting the.
【０００９】Ｒは水素原子、アルキル基などを示す。典
型的には水素原子である、アルキル基は炭素数１〜１
８、好ましくは１〜９、特に１〜３であり、シクロアル
キル基やアラルキル基であってもよい。典型的にはメチ
ルまたはエチルである。置換基数は２以下、好ましくは
０または１である。ｍは０または１である。[0009]R represents a hydrogen atom, aetc. alkylgroup. The alkyl group, which is typically a hydrogen atom, has 1 to 1 carbon atoms.
8, preferably 1 to 9, particularly 1 to 3, and may be a cycloalkyl group or an aralkyl group. Typically it is methyl or ethyl. Location substituent number 2 or less, preferably 0 or 1. m is 0 or1 .
【００１０】本発明に用いられるスチリル基またはシン
ナミル基を有する化合物の分子量は約１００〜８００、
特に約１００〜６００が好ましい。分子量が大きすぎる
とバイオゼリーの形成が不十分となり層厚が生長しな
い。また単に分子量のみでなく、スチリル当量またはシ
ンナミル当量が約１００〜約６００の範囲にあるのが好
ましい。The compound having a styryl group or a cinnamyl group used in the present invention has a molecular weight of about 100 to 800,
Particularly, about 100 to 600 is preferable. If the molecular weight is too large, the formation of biojelly becomes insufficient and the layer thickness does not grow. Further, it is preferable that not only the molecular weight but also the styryl equivalent or the cinnamyl equivalent is in the range of about 100 to about 600.
【００１１】本発明で用いられる化合物が桂皮酸系の場
合には、そのエステルまたは塩を用いてもよい。特に桂
皮酸エステルはバイオゼリーの生長に極めて有効であ
る。エステルとしては、分岐または直鎖の飽和または不
飽和の炭素数１〜１８、より好ましくは１〜１２、特に
１〜１０のアルコールとのエステルである。When the compound used in the present invention is cinnamic acid, its ester or salt may be used. In particular, cinnamic acid ester is extremely effective in growing biojelly. The ester is a branched or straight-chain saturated or unsaturated C 1-18, more preferably 1-12, especially 1-10 ester with an alcohol.
【００１２】塩としては無機または有機の塩いずれでも
よい。無機の塩としてはアルカリ金属、例えば、Ｎａ、
Ｋなどアルカリ土類金属塩、例えばＣａ、Ｍｇなど、ア
ンモニウムその他Ｍｎ、Ｚｒ(０)、Ａｌ、Ｚｎ、Ｆｅな
どが例示される。有機塩としはアミン類、アルカノール
アミン類、ポリアミン類、Ｎ−複素環化合物、例えばイ
ミダゾリンなどが例示される。The salt may be either an inorganic salt or an organic salt. Inorganic salts include alkali metals such as Na,
Examples thereof include alkaline earth metal salts such as K, such as Ca and Mg, ammonium and other Mn, Zr (0), Al, Zn, Fe and the like. Examples of the organic salt include amines, alkanolamines, polyamines, N-heterocyclic compounds such as imidazoline.
【００１３】本発明においてバイオゼリー形成剤は適当
な塗料組成物中に配合し、水中に浸漬されて使用される
構造体表面に塗装する。適当な溶媒に溶解もしくは分散
させ必要によりポリマーを加え、漁網用塗料として使用
することができる。In the present invention, the biojelly-forming agent is blended in a suitable coating composition and immersed in water for coating on the surface of the structure to be used. It can be used as a paint for fishing nets by dissolving or dispersing it in an appropriate solvent and adding a polymer if necessary.
【００１４】スライム層、特にバイオゼリー層は、バイ
オゼリー形成剤を含む塗料を塗装したり、含浸させ、あ
るいはこれを練り込んむなどの方法で処理した構造体を
水中に浸漬することによって形成させればよい。以下、
実施例をあげて本発明を説明する。The slime layer, particularly the biojelly layer, is formed by immersing the structure treated by a method such as coating, impregnating, or kneading a coating containing a biojelly-forming agent in water. Just do it. Less than,
The present invention will be described with reference to examples.
【００１５】実施例１〜２８ブチラール樹脂２０g、メチルエチルケトン１５gおよび
バイオゼリー形成剤１０gを均一に混合しバイオゼリー
形成塗料を調製した。この塗料を市販のアクリル板(３
００mm×１００mm×２mm)に乾燥塗膜厚さ約２００μmと
なるよう塗布乾燥し、これを水温約１２〜１８℃の海中
に浸漬し、形成されたバイオゼリー層の厚さおよび汚損
生物の付着状態を経時的に観察した。結果を表１に示
す。Examples 1 to 28 20 g of butyral resin, 15 g of methyl ethyl ketone and 10 g of biojelly forming agent were uniformly mixed to prepare a biojelly forming paint. Apply this paint to a commercially available acrylic plate (3
(00 mm x 100 mm x 2 mm) and dried to give a dry coating film thickness of about 200 μm, and then immerse this in the sea at a water temperature of about 12 to 18 ° C to form the thickness of the formed biojelly layer and the state of adhesion of fouling organisms. Was observed over time. The results are shown in Table 1.
【００１６】比較例１バイオゼリー形成剤に代えて従来の代表的防汚剤である
トリブチルスズオキシド(ＴＢＴＯ)７gを用いる以外、
実施例１と同様にして防汚塗料を調製し、これを市販の
アクリル板(３００mm×１００mm×２mm)に乾燥塗膜厚さ
２００μmとなるよう塗布乾燥し、これを水温約１２〜
１８℃の海中に浸漬し、形成されたバイオゼリー層の厚
さおよび汚損生物の付着状態を経時的に観察した。結果
を表１に示す。Comparative Example 1 In place of the biojelly forming agent, 7 g of tributyltin oxide (TBTO), which is a typical conventional antifouling agent, was used.
An antifouling paint was prepared in the same manner as in Example 1, and this was applied to a commercially available acrylic plate (300 mm x 100 mm x 2 mm) so as to have a dry coating film thickness of 200 µm and dried, and this was heated to a water temperature of about 12 to 12 ~.
The thickness of the formed bio-jelly layer and the adhered state of fouling organisms were observed with time by immersing in the sea at 18 ° C. The results are shown in Table 1.
【００１７】比較例２ブチラール樹脂２０gと亜酸化銅１５gおよびロジン２ｇ
をメチルエチルケトン１５ｇに均一に溶解し、比較例１
と同じ寸法のアクリル板上に乾燥塗膜厚さ約２００μm
となるよう塗布乾燥し、これを水温約１２〜１８℃の海
中に浸漬し、形成されたバイオゼリー層の厚さおよび汚
損生物の付着状態を経時的に観察した。結果を表１に示
す。Comparative Example 2 20 g of butyral resin, 15 g of cuprous oxide and 2 g of rosin
Was uniformly dissolved in 15 g of methyl ethyl ketone, and Comparative Example 1
Dry coating thickness of about 200μm on acrylic plate of the same size as
It was coated and dried so as to obtain the following, and this was immersed in the sea at a water temperature of about 12 to 18 ° C., and the thickness of the formed bio-jelly layer and the adhered state of fouling organisms were observed over time. The results are shown in Table 1.
【００１８】比較例３ブチラール樹脂２０gをメチルエチルケトン１５gに混合
しこれを市販のアクリル板(３００mm×１００mm×２mm)
に乾燥塗膜厚さ２００μmとなるよう塗布乾燥し、これ
を水温約１２〜１８℃の海中に浸漬し、形成されたバイ
オゼリー層の厚さおよび汚損生物の付着状態を経時的に
観察した。結果を表１に示す。Comparative Example 3 20 g of butyral resin was mixed with 15 g of methyl ethyl ketone, and this was mixed with a commercially available acrylic plate (300 mm × 100 mm × 2 mm).
The coating film was dried to give a dry coating film thickness of 200 μm, immersed in the sea at a water temperature of about 12 to 18 ° C., and the thickness of the formed biojelly layer and the adhered state of fouling organisms were observed over time. The results are shown in Table 1.
【００１９】比較例４〜７桂皮酸に代えて、キシレン、エチルベンゼン、ビニルシ
クロヘキサン、エチルシクロヘキサンをそれぞれ用いる
以外、実施例１と同様にしてバイオゼリーを形成させ
た。厚さ付着状態を経時的に観察し、これを表１に示し
た。Comparative Examples 4 to 7 Biojellies were formed in the same manner as in Example 1 except that xylene, ethylbenzene, vinylcyclohexane and ethylcyclohexane were used instead of cinnamic acid. The adhesion state of the thickness was observed with time, and is shown in Table 1.
【００２０】比較例８比較例１のアクリル板と同寸法のガラス板をそのまま水
温１２〜１８℃の海中に浸漬し、形成されたバイオゼリ
ーの層の厚さおよび汚損生物の付着状態を経時的に観察
した。結果を表１に示す。Comparative Example 8 A glass plate having the same dimensions as the acrylic plate of Comparative Example 1 was immersed in the sea at a water temperature of 12 to 18 ° C., and the thickness of the formed biojelly layer and the adhered state of fouling organisms were changed with time. Observed. The results are shown in Table 1.
【００２１】比較例９比較例１と同じ寸法のアクリル板をそのまま水温約１２
〜１８℃の海中に浸漬し、形成されたバイオゼリー層の
厚さおよび汚損生物の付着状態を経時的に観察した。結
果を表１に示す。Comparative Example 9 An acrylic plate having the same dimensions as in Comparative Example 1 was used as it was at a water temperature of about 12
The thickness of the formed bio-jelly layer and the adhered state of fouling organisms were observed with time by immersing in the sea at -18 ° C. The results are shown in Table 1.
【００２２】[0022]
【表１】[Table 1]
【００２３】実施例２９〜４６ (抗菌性試験)(１) 培地の調製: 検出用デイスク培地(極東株式会社
製)２％水溶液を１２０℃で３０分間滅菌し、その５重
量部に対しバシラス種(Ｂacillus sp)、ビブリオ種(Ｖ
ibrio sp)およびサルモネラ種(Ｓalmonella sp)の混
合培養ブイヨン培地１重量部を加え、滅菌シャーレ中に
流して寒天平面培地を調製した。(２) ペーパー・デイスクの調製: 試験物質としてバ
イオゼリー形成剤(２５mg)をアセトンに加えた。これを
直径７mmの東洋濾紙Ｎo．５３製デイスクをこの溶液に
含浸させ、乾燥して試験物質含浸ペーパー・デイスクを
調製した。(３) (２)のペーパー・デイスクを(１)の寒天平面培地
上に載せ、３０℃で５日間培養し、菌の成育が観察され
ない部分(阻止円)の直径を測定し、抗菌性を評価した。
結果を表２に示す。Examples 29 to 46 (Antibacterial test) (1) Preparation of medium: A 2% aqueous solution of a detection disk medium (manufactured by Kyokuto Co., Ltd.) was sterilized at 120 ° C. for 30 minutes, and 5 parts by weight of Bacillus spp. (Bacillus sp ), Vibrio spp. (V
ibrio sp ) and 1 part by weight of mixed culture broth medium ofSalmonella sp. (Salmonella sp ) were added and poured into a sterile petri dish to prepare an agar flat medium. (2) Preparation of paper disk: A biojelly forming agent (25 mg) was added to acetone as a test substance. This is a Toyo filter paper No. A 53-made disc was impregnated with this solution and dried to prepare a test substance-impregnated paper disc. (3) Place the paper disk of (2) on the agar flat medium of (1), incubate at 30 ° C for 5 days, and measure the diameter of the part (inhibition circle) where growth of bacteria is not observed, to determine antibacterial activity. evaluated.
The results are shown in Table 2.
【００２４】比較例１０バイオゼリー形成剤に代えて防汚剤(ビストリブチルス
ズオキシド(ＴＢＴＯ))を用いる以外実施例２９と同様
にして抗菌性を評価した。結果を表２に示す。Comparative Example 10 The antibacterial property was evaluated in the same manner as in Example 29 except that an antifouling agent (bistributyltin oxide (TBTO)) was used instead of the biojelly forming agent. The results are shown in Table 2.
【００２５】比較例１１試験物質として銅系防汚剤(亜酸化銅)を用いる以外実施
例２９と同様にして抗菌性を評価した。結果を表２に示
す。Comparative Example 11 The antibacterial property was evaluated in the same manner as in Example 29 except that a copper-based antifouling agent (cuprous oxide) was used as the test substance. The results are shown in Table 2.
【００２６】比較例１２〜１５バイオゼリー形成剤に代えてキシレン、エチルベンゼ
ン、ビニルシクロヘキサン、エチルシクロヘキサンをそ
れぞれ用いる以外、実施例２１と同様にして抗菌性を評
価した。結果を表２示す。Comparative Examples 12 to 15 Antibacterial properties were evaluated in the same manner as in Example 21 except that xylene, ethylbenzene, vinylcyclohexane and ethylcyclohexane were used instead of the biojelly forming agent. The results are shown in Table 2.
【００２７】比較例１６バイオゼリー形成剤を配合しない以外、実施例２９と同
様にして抗菌性を評価した。Comparative Example 16 The antibacterial property was evaluated in the same manner as in Example 29 except that the biojelly forming agent was not added.
【００２８】[0028]
【表２】[Table 2]
【００２９】[0029]
【発明の効果】水中構造体にバイオゼリー層を意図的に
形成させることによりフジツボ、セルブラ、カキ、ホヤ
などの大型水棲汚損生物の付着が有効に防止できる。ス
チリル系またはシンナミル系化合物を用いるとバイオゼ
リー層を厚く、かつ速く形成させることができる。スラ
イム層を厚くすることによって水棲汚濁生物の付着をよ
り一層効果的に行うことができる。Industrial Applicability By intentionally forming a biojelly layer on an underwater structure, it is possible to effectively prevent the attachment of large-scale aquatic fouling organisms such as barnacles, cellulas, oysters and squirts. When the styryl-based or cinnamyl-based compound is used, the biojelly layer can be formed thick and quickly. By increasing the thickness of the slime layer, the aquatic pollutant can be attached more effectively.
─────────────────────────────────────────────────────フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ａ０１Ｎ 37/44 Ａ０１Ｎ 37/44 55/00 55/00 Ｂ Ｃ０９Ｄ 5/16 Ｃ０９Ｄ 5/16 7/12 7/12 (72)発明者 大杉 宏治 大阪府寝屋川市池田中町19番17号 日本 ペイント株式会社内 (56)参考文献 特開 昭61−64768（ＪＰ，Ａ) 特開 平４−306269（ＪＰ，Ａ) 米国特許2398069（ＵＳ，Ａ) 米国特許3803885（ＵＳ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) A01N 27/00 A01N 29/04 A01N 33/06 A01N 35/02 A01N 37/34 A01N 37/44 A01N 55/00 C09D 5/16 C09D 7/12 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl.7 Identification Code FI A01N 37/44 A01N 37/44 55/00 55/00 B C09D 5/16 C09D 5/16 7/12 7/12 (72) Inventor Koji Osugi 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (56) Reference JP 61-64768 (JP, A) JP 4-306269 (JP, A) US Patent 2398069 ( US, A) U.S. Pat. No. 3,803,885 (US, A) (58) Fields investigated (Int.Cl.7 , DB name) A01N 27/00 A01N 29/04 A01N 33/06 A01N 35/02 A01N 37/34 A01N 37 / 44 A01N 55/00 C09D 5/16 C09D 7/12 CA (STN) REGISTRY (STN)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22202994AJP3404147B2 (en) | 1994-09-16 | 1994-09-16 | Bio jelly forming agent |
| CA002158191ACA2158191A1 (en) | 1994-09-16 | 1995-09-13 | Method for preventing settlement of aquatic fouling organisms |
| DK95114429TDK0702065T3 (en) | 1994-09-16 | 1995-09-14 | Method for preventing colonization of aquatic fouling organisms |
| EP95114429AEP0702065B1 (en) | 1994-09-16 | 1995-09-14 | Method for preventing settlement of aquatic fouling organisms |
| EP01110545AEP1123950B1 (en) | 1994-09-16 | 1995-09-14 | Method for preventing settlement of aquatic fouling organisms |
| DE69532214TDE69532214D1 (en) | 1994-09-16 | 1995-09-14 | Process for preventing sedimentation of polluting aquatic organisms |
| DE69524164TDE69524164T2 (en) | 1994-09-16 | 1995-09-14 | Process for preventing sedimentation of polluting aquatic organisms |
| DK01110545TDK1123950T3 (en) | 1994-09-16 | 1995-09-14 | Method of preventing the colonization of aquatic fouling organisms |
| US08/530,405US5861435A (en) | 1994-09-16 | 1995-09-15 | Method for preventing settlement of aquatic fouling organisms |
| AU30663/95AAU3066395A (en) | 1994-09-16 | 1995-09-15 | Method for preventing settlement of aquatic fouling organisms |
| KR1019950030215AKR100363364B1 (en) | 1994-09-16 | 1995-09-15 | How to Prevent Aquatic Organic Matter |
| KR1020020029934AKR100391528B1 (en) | 1994-09-16 | 2002-05-29 | Antifouling agents for preventing settlement of aquatic fouling organisms |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22202994AJP3404147B2 (en) | 1994-09-16 | 1994-09-16 | Bio jelly forming agent |
| Publication Number | Publication Date |
|---|---|
| JPH0885770A JPH0885770A (en) | 1996-04-02 |
| JP3404147B2true JP3404147B2 (en) | 2003-05-06 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22202994AExpired - LifetimeJP3404147B2 (en) | 1994-09-16 | 1994-09-16 | Bio jelly forming agent |
| Country | Link |
|---|---|
| JP (1) | JP3404147B2 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2398069A (en) | 1943-02-12 | 1946-04-09 | Stoner Mudge Inc | Antifouling composition |
| US3803885A (en) | 1969-09-25 | 1974-04-16 | Millmaster Onyx Corp | Control of algae in industrial water |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2398069A (en) | 1943-02-12 | 1946-04-09 | Stoner Mudge Inc | Antifouling composition |
| US3803885A (en) | 1969-09-25 | 1974-04-16 | Millmaster Onyx Corp | Control of algae in industrial water |
| Publication number | Publication date |
|---|---|
| JPH0885770A (en) | 1996-04-02 |
| Publication | Publication Date | Title |
|---|---|---|
| CA2178500C (en) | Aquatic antifouling compositions and methods | |
| US6692557B1 (en) | Antifouling of shellfish and aquaculture apparatus | |
| US5248221A (en) | Antifouling coating composition comprising lactone compounds, method for protecting aquatic structures, and articles protected against fouling organisms | |
| US5259701A (en) | Antifouling coating composition comprising furan compounds, method for protecting aquatic structures, and articles protected against fouling organisms | |
| US5154747A (en) | Antifouling composition using alkyl-phenols | |
| KR100363364B1 (en) | How to Prevent Aquatic Organic Matter | |
| US5334389A (en) | Antifouling coating and method for using same | |
| JP2005255858A (en) | Antifouling resin, method for producing the same, and antifouling paint | |
| WO1994008904A1 (en) | Antifouling coating composition and method | |
| JP3404147B2 (en) | Bio jelly forming agent | |
| US5252630A (en) | Antifouling coating and method for using same | |
| JP3034053B2 (en) | Use of organoboron compounds as antifouling agents | |
| JP3342965B2 (en) | Bio jelly forming agent | |
| JP3390543B2 (en) | Bio jelly forming agent | |
| JPH0885767A (en) | Antifouling coating material | |
| JPH08133920A (en) | Method for preventing attachment of aquatic fouling organisms | |
| CN1772826A (en) | Antifouling coating with low surface energy for marine mesh cage cover | |
| JP2759522B2 (en) | Underwater biofouling repellent antifouling paint composition | |
| Chen et al. | Polymer Composite Coating for Anti‐marine and Related Organism Corrosion | |
| JPS6357503A (en) | Antifouling agent for aquatic life | |
| JPH10175803A (en) | Antifouling material | |
| JPH08119808A (en) | Organism stick-proofing agent and antifouling coating containing the same | |
| AU723361B2 (en) | Antifouling of shellfish and aquaculture apparatus | |
| JP5168627B2 (en) | Bioassay method using Tanais | |
| JPH06179603A (en) | Antifouling agent for hulls and fishing nets |
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees | Free format text:JAPANESE INTERMEDIATE CODE: R250 | |
| R250 | Receipt of annual fees | Free format text:JAPANESE INTERMEDIATE CODE: R250 | |
| FPAY | Renewal fee payment (event date is renewal date of database) | Free format text:PAYMENT UNTIL: 20080229 Year of fee payment:5 | |
| FPAY | Renewal fee payment (event date is renewal date of database) | Free format text:PAYMENT UNTIL: 20090228 Year of fee payment:6 | |
| FPAY | Renewal fee payment (event date is renewal date of database) | Free format text:PAYMENT UNTIL: 20100228 Year of fee payment:7 | |
| FPAY | Renewal fee payment (event date is renewal date of database) | Free format text:PAYMENT UNTIL: 20100228 Year of fee payment:7 | |
| FPAY | Renewal fee payment (event date is renewal date of database) | Free format text:PAYMENT UNTIL: 20110228 Year of fee payment:8 | |
| FPAY | Renewal fee payment (event date is renewal date of database) | Free format text:PAYMENT UNTIL: 20120229 Year of fee payment:9 | |
| FPAY | Renewal fee payment (event date is renewal date of database) | Free format text:PAYMENT UNTIL: 20120229 Year of fee payment:9 | |
| FPAY | Renewal fee payment (event date is renewal date of database) | Free format text:PAYMENT UNTIL: 20130228 Year of fee payment:10 | |
| FPAY | Renewal fee payment (event date is renewal date of database) | Free format text:PAYMENT UNTIL: 20140228 Year of fee payment:11 | |
| R250 | Receipt of annual fees | Free format text:JAPANESE INTERMEDIATE CODE: R250 | |
| EXPY | Cancellation because of completion of term |