JP4601739B2 - Antifouling agent composition, antifouling paint containing the same, antifouling coating film, antifouling treatment using them, and antifouling method - Google Patents
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【０００１】
【産業上の利用分野】
本発明は、水棲生物の付着を防止するのに有用な、防汚剤組成物、その防汚剤組成物を用いた防汚塗膜、防汚処理物ならびに防汚方法に関する。詳しくは、本発明は、フジツボ、イガイ、セルブラ、ホヤ、藻類およびヒドロ虫などの水棲生物が、船底および漁網などに付着するのを防止するのに有用な防汚剤組成物、その防汚剤組成物を用いた、防汚塗膜、防汚処理物ならびに防汚方法に関する。
【０００２】
【発明の技術的背景】
防汚処理を施さない船舶、水中構築物、漁網ならびに漁具などは、水中に長期間さらされることにより、フジツボ、イガイ、セルブラ、ホヤ、藻類およびヒドロ虫などの水棲生物が付着・繁殖して、外観が損なわれるほか、多くの問題を生じることがある。
【０００３】
たとえば、船舶の船底に水棲生物が付着した場合には、外観が損なわれるほか、船全体の表面粗度が増加して、船速の低下、燃費の拡大、操縦性の低下、船底表面部の破損をなどを招くことがある。また、付着した水棲生物を船底から取り除くには、多大な労力、作業時間が必要となる。またたとえば、腐食防止などの表面処理の施された水中構造物に水棲生物が付着・繁殖し、その腐食防止用の塗膜などを損傷すると、その水中構造物の強度や機能が低下し寿命が著しく低下する等の被害が生ずることがある。さらに、たとえば漁網に水棲生物が付着した場合には、網目が塞がり水の流出入を阻害し、引き上げなどの作業が困難になるほか、漁網が養殖用漁網である場合には、内部の養殖魚が酸素不足で死亡するなどの問題が生じることがある。
【０００４】
このため、従来から水棲生物の付着を防止する薬剤の使用が図られていた。従来、船底用防汚塗料に用いられる防汚剤としては、亜酸化銅、有機スズ化合物、チオカルバミン酸塩、ロダン化銅、酸化亜鉛、銅ピリチオン、ジンクピリチオン、４，５−ジクロロ−２−ｎ−オクチルイソチアゾリン−３−オン、２−メチルチオ−４−６−ブチルアミノＳトリアジン、ピリジントリフェニルボロンなどが使用されてきた。また、漁網用の防汚剤としては、テトラエチルチウラムジスルフィド、ビスダイセン、銅粉、マレイミド類、ピリジントリフェニルボロン等が使用され、最近ではこれらに加えて、トリフェニルボロンアルキルアミン塩等が使用されている。
【０００５】
しかしながら、このような従来の防汚剤のうち、有機錫化合物には、毒性が強く、海洋汚染、奇形魚類や奇形貝類の発生、食物連鎖による生態系への悪影響などが懸念されている。また、亜酸化銅（Ｃｕ2Ｏ）は、低毒性であるため古くから用いられているが不安定な物質であって、海水中で酸化されて次第に二価の銅塩に変化し、防汚作用が徐々に低下するという問題があるほか、防汚剤として塗料中に含有させた状態で長期保存ができないという問題がある。
【０００６】
このような問題を解決した防汚剤として、一価の銅を含有する溶解性ガラスを用いた防汚剤（特開昭６２−１５８２０２号公報）および防汚塗料（特開昭６３−４８３６６号公報）が提案されていた。これらの防汚剤および防汚塗料は、防汚作用に優れ、低毒性である一価の銅を安定化させ、長期にわたって防汚作用を有するものである。
【０００７】
しかしながらこれらの防汚剤は、単独で用いても、また併用して用いても、特定もしくは数種の海中生物の付着防止にしか効果がないなど、選択性があり、その他の水中生物には防汚効果を持たない場合がある。
このため毒性が低く、長期にわたって防汚作用を有し、フジツボ、イガイ、セルブラ、ホヤ、藻類およびヒドロ虫などの主要な広範囲の水棲生物に対して防汚効果を有する防汚剤組成物の開発が求めらていた。
【０００８】
【発明の目的】
本発明は、毒性が低く、長期にわたって防汚作用を有し、フジツボ、イガイ、セルブラ、ホヤ、藻類およびヒドロ虫などの主要な水棲生物に対して防汚効果を有する防汚剤組成物、およびそれを用いた防汚塗膜、防汚処理物ならびに防汚方法を提供することを目的とする。
【０００９】
【発明の概要】
本発明の防汚剤組成物は、
（ａ）溶解性銅ガラスと、
（ｂ）金属ピリチオン類と
を含有することを特徴としている。
【００１０】
また本発明の別の防汚剤組成物は、
（ａ）溶解性銅ガラス、
（ｂ）金属ピリチオン類
および
（ｃ）Ｎ，Ｎ−ジメチルジクロロフェニル尿素、２，４，６−トリクロロフェニルマレイミド、２−メチルチオ−４−ｔｅｒｔ−ブチルアミノ−６−シクロプロピルアミノＳトリアジン、４，５−ジクロロ−２−ｎ−オクチル−イソチアゾリン−３−オンおよび２，４，５，６−テトラクロロイソフタロニトリルからなる群から選ばれる少なくとも１種の有機防汚剤
を含有することを特徴としている。
【００１１】
本発明の防汚塗料は、上記のような防汚剤組成物を含有することを特徴としている。
本発明の防汚塗膜は、上記のような防汚塗料から形成されることを特徴としている。
本発明の防汚処理物は、水中構造体、船舶、漁網または漁具を上記のような防汚塗料または防汚塗膜で、被覆または処理したことを特徴としている。
【００１２】
またさらに、本発明の防汚方法は、海水または真水と接触する水中構造体、船舶、漁網または漁具を、上記のような防汚塗料または防汚塗膜で、被覆または処理することを特徴としている。
【００１３】
【発明の具体的説明】
以下、本発明について具体的に説明する。
本発明の防汚剤組成物は、（ａ）溶解性銅ガラスと、（ｂ）金属ピリチオン類とを含有している。
本発明において、溶解性銅ガラス（ａ）とは、一価の銅を含有する溶解性ガラスである。溶解性ガラスとは、ガラス成分が溶融しやすいガラスであり、ＳｉＯ2、Ｂ2Ｏ3、およびＰ2Ｏ5から選ばれる一種以上の網目形成酸化物と、Ｎａ2Ｏ、Ｋ2Ｏ、ＣａＯ、ＭｇＯ、ＢａＯ、Ａｌ2Ｏ3などの網目修飾酸化物とから形成され、これらの成分の組成比によって溶解度を制御することができるものである。この溶解性ガラス中において、一価の銅は、ガラスマトリクス成分または微結晶として、Ｃｕ+イオンまたはＣｕ2Ｏ微粒子の形態で安定に存在し、ガラス成分の溶解に応じて徐々に表面から溶出する。
【００１４】
このような溶解性銅ガラス（ａ）は、長期にわたって防汚作用を有し、かつ防汚作用に有効な一価の銅を安定に保持し、また一価の銅の溶出量も制御することができる。
上記溶解性銅ガラス（ａ）および金属ピリチオン類（ｂ）を含む本発明の防汚剤組成物は、その組成を特に限定するものではないが、溶解性銅ガラス（ａ）１００重量部に対して、金属ピリチオン類（ｂ）を１〜２００重量部、好ましくは５〜５０重量部含有するのが好ましい。
【００１５】
また、本発明の別の防汚剤組成物は、上記溶解性銅ガラス（ａ）と、金属ピリチオン類（ｂ）と、特定の有機防汚剤（ｃ）とを含有している。このような特定の有機防汚剤（ｃ）としては、Ｎ，Ｎ−ジメチルジクロロフェニル尿素、２，４，６−トリクロロフェニルマレイミド、２−メチルチオ−４−ｔｅｒｔ−ブチルアミノ−６−シクロプロピルアミノＳトリアジン、４，５−ジクロロ−２−ｎ−オクチル−イソチアゾリン−３−オンおよび２，４，５，６−テトラクロロイソフタロニトリルが挙げられ、これらより選ばれる１種以上をいずれも好ましく用いることができる。
【００１６】
本発明の防汚剤組成物が、上記溶解性銅ガラス（ａ）と、金属ピリチオン類（ｂ）と、特定の有機防汚剤（ｃ）とを含有する場合には、その組成を特に限定するものではないが、溶解性銅ガラス（ａ）１００重量部に対して、金属ピリチオン類（ｂ）を１〜２００重量部、好ましくは５〜５０重量部含有し、上記有機防汚剤（ｃ）を１〜２００重量部、好ましくは５〜５０重量部含有するのが望ましい。
【００１７】
本発明において金属ピリチオン類（ｂ）としては、銅ピリチオン、ジンクピリチオンなどが挙げられ、これらをいずれも好適に使用することができるが、銅ピリチオンを用いるのが特に好ましい。
また、本発明の防汚剤組成物は、銅または無機銅化合物（ｄ）を含有してもよい。無機銅化合物としては、亜酸化銅、ロダン化銅などが挙げられる。本発明の防汚剤組成物が、銅または無機銅化合物（ｄ）を含有する場合の、銅または無機銅化合物（ｄ）量は特に限定されるものではないが、溶解性銅ガラス（ａ）１００重量部に対して、銅または無機銅化合物（ｄ）を１０〜１０００重量部、好ましくは５０〜５００重量部含有するのが望ましい。
【００１８】
さらに本発明の防汚剤組成物は、樹脂成分（ｅ）を含有してもよい。樹脂成分（ｅ）としては、アクリル系樹脂、ビニル樹脂、変性ビニル樹脂、スチレン−ブタジエン系樹脂およびポリシロキサン系樹脂が挙げられ、これらより選ばれる１種以上をいずれも好ましく用いることができる。これらの樹脂は、樹脂構造内に金属を含有した金属含有樹脂であってもよい。
【００１９】
さらにまた、本発明の防汚剤組成物は、溶出助剤（ｆ）を含有してもよい。溶出助剤（ｆ）としては、ロジン、塩素化パラフィン、リン酸トリクレジル、ポリブテン、シリコーンオイル、パラフィンおよびワセリンが挙げられ、これらより選ばれる１種以上をいずれも好ましく用いることができる。
このような構成による本発明の防汚剤組成物は、毒性が低く、また長期にわたって防汚作用を有し、さらにフジツボ、イガイ、セルブラ、ホヤ、藻類およびヒドロ虫などの主要な広範囲の水棲生物に対して高い防汚効果を有するものであって、水中での防汚性を要するものの表面に対して、防汚処理を施すために用いることができる。
【００２０】
本発明の防汚剤組成物は、液状、ペレット状、スラリー状、粉末状など、どのような形態であってもよく、防汚処理を施す対象により適宜選択して用いることができる。また、本発明の防汚剤組成物は、着色用の塗料など、防汚目的以外の各種表面処理剤と混合して用いてもよい。
本発明では、このような防汚剤組成物を防汚塗料として用いるのが特に好ましい。防汚塗料は、塗布、浸漬、スプレーなどの処理を行うものであって、被処理物および用途などによって、適宜粘度などを調整したものが用いられる。たとえば、漁網を浸漬して処理する場合、スプレー塗布を行う場合などには、比較的低粘度の防汚塗料を用いることができる。
【００２１】
また、このような本発明の防汚剤組成物は、長期間水と接触するものに対して防汚処理を施す用途に有効に使用することができ、海水または真水と接触する船舶、水中構造体、漁網または漁具の表面を、上記のような防汚塗料で被覆または処理することにより、該表面に良好な防汚性を付与することができる。
本発明の防汚方法は、海水または真水と接触する船舶、水中構造体、漁網または漁具などの被処理物の表面を本発明の防汚塗料で被覆または処理する方法であって、本発明の防汚塗料を用いて該表面に防汚性を与えることができる方法であれば特に限定されるものではなく、たとえば、塗布、接着、浸漬などの常法により行うことができる。
【００２２】
また本発明の防汚塗料は、上記のようなの防汚剤組成物を含有している。このような防汚塗料は、水中構造体、船舶、漁網あるいは漁具などの被処理物の表面に防汚性を付与する防汚処理に好適に用いることができる。本発明の防汚塗料は、上記のようなの防汚剤組成物の他に、所望に応じて適宜、溶剤、樹脂、顔料などを含有してもよく、たとえば船舶の船底処理に用いる場合には樹脂を多く含有させてもよく、また、漁網処理に用いる場合には、漁網を浸漬して処理することができるよう、溶剤を多く含有させてもよい。
【００２３】
本発明の防汚塗膜は、上記のようなの防汚塗料から形成されている。このような防汚塗膜は、海水または真水と接触する水中構造体、船舶、漁網あるいは漁具などの被処理物の表面に、上記のような防汚塗料を塗布し、適宜乾燥するなどの通常の方法によって形成することができる。また、本発明の防汚塗膜は、被処理物以外の物質の表面に上記のような防汚塗料を塗布し、乾燥後に剥離するなどの方法によって形成したフィルム状物であってもよく、布などの塗膜基材表面に上記のような防汚塗料を塗布、乾燥するなどの方法によって形成した塗膜構造物であってもよい。
【００２４】
本発明の防汚処理物は、上記のような防汚塗膜で水中構造体、船舶、漁網または漁具を被覆した防汚処理物である。この防汚処理物は、被処理物である船舶または水中構造体の一部または全体を、上記のような防汚塗膜で被覆したものであればよいが、上記のような防汚塗料を塗布して防汚塗膜を形成させるか、上記フィルム状に形成した防汚塗膜または塗膜構造物を接着するかの方法により形成することができる。
【００２５】
【発明の効果】
本発明によれば、毒性が低く、長期にわたって防汚作用を有し、フジツボ、イガイ、セルブラ、ホヤ、藻類およびヒドロ虫などの主要な水棲生物に対して防汚効果を有する防汚剤組成物を得ることができる。また、本発明の防汚剤組成物を含有する、良好な防汚性を示す防汚塗料、防汚塗膜および防汚処理物を提供することができ、さらに、効果的な防汚方法を提供することができる。
【００２６】
【実施例】
以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
【００２７】
【実施例１】
ＳｉＯ2：７．７重量部、Ａｌ2Ｏ3：０．１重量部、Ｎａ2Ｏ：５．９重量部、Ｂ2Ｏ3：２８．８重量部、Ｃｕ2Ｏ：５３．３重量部および、ＺｎＯ：４．２重量部の組成で、溶解性銅ガラスを調製した。この溶解性銅ガラスを用いて、表１に示す組成で原料を混合し、防汚塗料Ａを調製した。得られた防汚塗料Ａは保存安定性が良好であった。
【００２８】
次に、得られた防汚塗料Ａを、１００×３００×３ｍｍの寸法の塩化ビニル板に、乾燥膜厚が２００±２０μｍとなるようにアプリケーターで塗布して乾燥させ、防汚塗膜を有する防汚処理物Ａを調製した。
この防汚処理物Ａを、広島県宮島沖の海中の水深５０ｃｍに浸漬し、６ヶ月ごとに水棲生物の付着面積の割合を調査した。結果を表２に示す。
【００２９】
表２より、防汚処理物Ａは、１８ヶ月の長期間においても水棲生物の付着が見られず、長期にわたり良好な防汚性を有していることがわかる。このように、（ａ）溶解性銅ガラスと（ｂ）金属ピリチオン類とを含有する本発明の防汚剤組成物を用いた防汚塗料Ａからは、長期にわたり高い防汚効果を有する、防汚塗膜および防汚処理物が得られていることがわかる。
【００３０】
【実施例２】
実施例１で調製した溶解性銅ガラスを用い、表１に示す組成で原料を混合し、防汚塗料Ｂを調製した。得られた防汚塗料Ｂは保存安定性が良好であった。
次に、防汚塗料Ｂを用いたことの他は、実施例１と同様にして防汚処理物Ｂを調製し、さらに実施例１と同様にして水棲生物の付着面積の割合を調査した。結果を表２に示す。
【００３１】
表２より、防汚処理物Ｂは、１８ヶ月の長期間においても水棲生物の付着が見られず、長期にわたり良好な防汚性を有していることがわかる。このように、（ａ）溶解性銅ガラス、（ｂ）金属ピリチオン類および（ｃ）特定の有機防汚剤とを含有する本発明の防汚剤組成物を用いた防汚塗料Ｂからは、長期にわたり高い防汚効果を有する、防汚塗膜および防汚処理物が得られていることがわかる。
【００３２】
【比較例１、２】
表１に示す組成で原料を混合し、防汚塗料ＤおよびＥをそれぞれ調製した。
次に、調製した各防汚塗料を用いたことの他は、実施例１と同様にして防汚処理物ＤおよびＥをそれぞれ調製し、さらに実施例１と同様にして水棲生物の付着面積の割合を調査した。結果を表２に示す。
【００３３】
表２より、防汚処理物ＤおよびＥは、浸漬期間６ヶ月では良好な防汚性を示しているが、浸漬期間１２ヶ月以上では水棲生物の付着が見られ、防汚性が低下していることがわかる。浸漬期間１２ヶ月および１８ヶ月において付着した水棲生物は、フジツボ、白うすボヤ、セハプラおよびノリであった。
【００３４】
【表１】
【表２】
【実施例３】
実施例１で調製した溶解性銅ガラスを用い、表３に示す組成で原料を混合し、漁網用防汚塗料Ｃを調製した。この防汚塗料Ｃは保存安定性が良好であった。
次に、ポリエチレン製無結節網（７節、４００デニール、５０本）を、得られた防汚塗料Ｃに浸漬塗布して乾燥させ、防汚処理物Ｃを調製した。
【００３７】
この防汚処理物Ｃを、平成１０年３月１０日より１０月１０日までの６ヶ月間、高知県宿毛湾の水深２ｍに浸漬し、水棲生物の付着状況を調査した。結果を表４に示す。
表４より、（ａ）溶解性銅ガラスと（ｂ）金属ピリチオン類とを含む、本発明の防汚剤組成物を用いた漁網用防汚塗料Ｃで処理して得られた防汚処理物Ｃ（防汚処理漁網）には、フジツボ、ホヤ・セルブラ、ヒドラの、いずれの種の水棲生物についても付着が見られず、良好な防汚性を有する防汚処理物が得られていることがわかる。
【００３８】
【比較例３〜５】
表３に示す組成で原料を混合し、漁網用防汚塗料Ｆ、Ｇ、Ｈをそれぞれ調製した。
次に、調製した各防汚塗料を用いたことの他は実施例３と同様にして、防汚処理物Ｆ、Ｇ、Ｈをそれぞれ調製した。さらに、得られた各防汚処理物について、実施例３と同様にして水棲生物の付着状況を調査した。結果を表４に示す。
【００３９】
表４より、比較例３および５では、調査した水棲生物全種の付着が見られ、防汚性に劣ることがわかる。また、比較例４では、ヒドラについては選択的に防汚性を示しているが、他の水棲生物に対しての防汚性は示しておらず、防汚効果に選択性があり、防汚性に劣ることがわかる。
【００４０】
【表３】
【表４】
以上の実施例および比較例に示されるように、（ａ）溶解性銅ガラスと（ｂ）金属ピリチオン類とを含む本発明の防汚剤組成物、または（ａ）溶解性銅ガラス、（ｂ）金属ピリチオン類および（ｃ）有機防汚剤とを含む本発明の防汚剤組成物は、長期にわたって防汚作用を有し、フジツボ、イガイ、セルブラ、ホヤ、藻類およびヒドロ虫などの主要な水棲生物に対して防汚効果を有することがわかる。[0001]
[Industrial application fields]
The present invention relates to an antifouling agent composition useful for preventing adhesion of aquatic organisms, an antifouling coating film using the antifouling agent composition, an antifouling treatment product, and an antifouling method. Specifically, the present invention relates to an antifouling composition useful for preventing aquatic organisms such as barnacles, mussels, selbra, sea squirts, algae, and hydroworms from adhering to the bottom of a ship and fishing nets, and the antifouling agent thereof. The present invention relates to an antifouling coating film, an antifouling treatment product and an antifouling method using the composition.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
Ships, underwater structures, fishing nets, and fishing gear that are not subjected to antifouling treatment are exposed to aquatic organisms such as barnacles, mussels, selbra, sea squirts, algae, and hydroworms when they are exposed to water for a long time. Damages and can cause many problems.
[0003]
For example, when aquatic organisms adhere to the bottom of a ship, the appearance is impaired, and the surface roughness of the entire ship increases, resulting in a decrease in ship speed, an increase in fuel consumption, a decrease in maneuverability, It may cause damage. Moreover, a great deal of labor and work time are required to remove the attached aquatic organisms from the ship bottom. For example, if aquatic organisms adhere to and propagate on an underwater structure that has undergone surface treatment such as corrosion prevention, and damages the corrosion-preventing coating film, etc., the strength and function of the underwater structure will decrease and the life will be reduced. Damage such as a significant decrease may occur. In addition, for example, when aquatic organisms adhere to a fishing net, the mesh is blocked and the inflow and outflow of water is obstructed, making it difficult to pull up. In addition, if the fishing net is an aquaculture net, May die due to lack of oxygen.
[0004]
For this reason, use of the chemical | medical agent which prevents adhesion | attachment of aquatic organisms conventionally was aimed at. Conventionally, antifouling agents used for antifouling paints for ship bottoms include cuprous oxide, organotin compounds, thiocarbamates, copper dandanates, zinc oxide, copper pyrithione, zinc pyrithione, 4,5-dichloro-2-n. -Octylisothiazolin-3-one, 2-methylthio-4-6-butylamino S triazine, pyridine triphenylboron and the like have been used. In addition, as antifouling agents for fishing nets, tetraethylthiuram disulfide, bisdaicene, copper powder, maleimides, pyridine triphenylboron, etc. are used, and recently, in addition to these, triphenylboron alkylamine salts are used. Yes.
[0005]
However, among such conventional antifouling agents, organotin compounds are highly toxic, and there are concerns about marine pollution, the occurrence of malformed fish and malformed shellfish, and the adverse effects on the ecosystem caused by the food chain. Cuprous oxide (Cu 2 O) is an unstable substance that has been used for a long time because of its low toxicity. It is oxidized in seawater and gradually changes to a divalent copper salt. In addition to the problem that the action gradually decreases, there is a problem that it cannot be stored for a long time when it is contained in the paint as an antifouling agent.
[0006]
As an antifouling agent that solves such problems, an antifouling agent (JP-A 62-158202) and an anti-fouling paint (JP 63-48366) using a soluble glass containing monovalent copper are used. Publication) was proposed. These antifouling agents and antifouling paints stabilize monovalent copper which is excellent in antifouling action and has low toxicity, and has an antifouling action over a long period of time.
[0007]
However, these antifouling agents are selective, whether they are used alone or in combination, and are only effective in preventing the adhesion of specific or several types of marine organisms. There may be no antifouling effect.
Therefore, development of an antifouling agent composition having low toxicity, having antifouling action for a long period of time, and having antifouling effect on a wide range of major aquatic organisms such as barnacles, mussels, selbra, squirts, algae and hydroworms. Wanted.
[0008]
OBJECT OF THE INVENTION
The present invention provides an antifouling composition having low toxicity, having an antifouling action for a long period of time, and having an antifouling effect on major aquatic organisms such as barnacles, mussels, selbra, squirts, algae and hydroworms, and An object is to provide an antifouling coating film, an antifouling treatment product and an antifouling method using the same.
[0009]
SUMMARY OF THE INVENTION
Antifouling agent composition of the present invention,
(A) soluble copper glass;
(B) It contains metal pyrithione.
[0010]
Another antifouling composition of the present invention is
(A) soluble copper glass,
(B) metal pyrithiones and (c) N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino S-triazine, 4,5 It contains at least one organic antifouling agent selected from the group consisting of -dichloro-2-n-octyl-isothiazolin-3-one and 2,4,5,6-tetrachloroisophthalonitrile .
[0011]
The antifouling paint of the present invention is characterized by containing the antifouling agent composition as described above.
The antifouling coating film of the present invention is formed from the antifouling paint as described above.
The antifouling treatment product of the present invention is characterized in that an underwater structure, ship, fishing net or fishing gear is covered or treated with the above antifouling paint or antifouling coating film.
[0012]
Furthermore, the antifouling method of the present invention is characterized by covering or treating an underwater structure, ship, fishing net or fishing gear that contacts seawater or fresh water with the antifouling paint or antifouling coating film as described above. Yes.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be specifically described.
The antifouling agent composition of the present invention contains (a) soluble copper glass and (b) metal pyrithione.
In the present invention, the soluble copper glass (a) is a soluble glass containing monovalent copper. The soluble glass is a glass in which glass components are easily melted, and one or more network-forming oxides selected from SiO 2 , B 2 O 3 , and P 2 O 5 , Na 2 O, K 2 O, and CaO. , MgO, BaO, Al 2 O 3 and other network-modified oxides, and the solubility can be controlled by the composition ratio of these components. In this soluble glass, monovalent copper is stably present in the form of Cu + ions or Cu 2 O fine particles as a glass matrix component or microcrystal, and gradually elutes from the surface as the glass component dissolves. .
[0014]
Such soluble copper glass (a) has an antifouling action for a long period of time, stably holds monovalent copper effective for the antifouling action, and controls the elution amount of monovalent copper. Can do.
Although the antifouling agent composition of the present invention containing the soluble copper glass (a) and the metal pyrithione (b) is not particularly limited, the composition is based on 100 parts by weight of the soluble copper glass (a). The metal pyrithione (b) is preferably contained in an amount of 1 to 200 parts by weight, preferably 5 to 50 parts by weight.
[0015]
Another antifouling composition of the present invention contains the soluble copper glass (a), the metal pyrithione (b), and a specific organic antifouling agent (c). Examples of such a specific organic antifouling agent (c) include N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino S. Examples include triazine, 4,5-dichloro-2-n-octyl-isothiazolin-3-one, and 2,4,5,6-tetrachloroisophthalonitrile, and one or more selected from these are preferably used. Can do.
[0016]
When the antifouling agent composition of the present invention contains the soluble copper glass (a), the metal pyrithiones (b), and the specific organic antifouling agent (c), the composition is particularly limited. The organic antifouling agent (c) contains 1 to 200 parts by weight, preferably 5 to 50 parts by weight of the metal pyrithione (b) with respect to 100 parts by weight of the soluble copper glass (a). 1) to 200 parts by weight, preferably 5 to 50 parts by weight.
[0017]
In the present invention, examples of the metal pyrithione (b) include copper pyrithione, zinc pyrithione and the like, and any of these can be suitably used, but it is particularly preferable to use copper pyrithione.
Moreover, the antifouling agent composition of the present invention may contain copper or an inorganic copper compound (d). Examples of inorganic copper compounds include cuprous oxide and copper dandanide. The amount of copper or inorganic copper compound (d) when the antifouling agent composition of the present invention contains copper or inorganic copper compound (d) is not particularly limited, but soluble copper glass (a) It is desirable to contain 10 to 1000 parts by weight, preferably 50 to 500 parts by weight of copper or inorganic copper compound (d) with respect to 100 parts by weight.
[0018]
Furthermore, the antifouling agent composition of the present invention may contain a resin component (e). Examples of the resin component (e) include acrylic resins, vinyl resins, modified vinyl resins, styrene-butadiene resins, and polysiloxane resins, and any one or more selected from these can be preferably used. These resins may be metal-containing resins containing a metal in the resin structure.
[0019]
Furthermore, the antifouling agent composition of the present invention may contain an elution aid (f). Examples of the dissolution aid (f) include rosin, chlorinated paraffin, tricresyl phosphate, polybutene, silicone oil, paraffin, and petrolatum, and any one or more selected from these can be preferably used.
The antifouling agent composition of the present invention having such a constitution has low toxicity and has an antifouling action for a long period of time, and further, a wide range of major aquatic organisms such as barnacles, mussels, selbra, squirts, algae and hydroworms It has a high antifouling effect against water and can be used to perform antifouling treatment on the surface of the one requiring antifouling properties in water.
[0020]
The antifouling agent composition of the present invention may be in any form such as liquid, pellet, slurry, and powder, and can be appropriately selected and used depending on the object to be subjected to the antifouling treatment. Further, the antifouling agent composition of the present invention may be used by mixing with various surface treatment agents other than antifouling purposes such as a paint for coloring.
In the present invention, it is particularly preferable to use such an antifouling composition as an antifouling paint. The antifouling paint is used for treatment such as coating, dipping, spraying, and the like, and the viscosity is appropriately adjusted depending on the object to be treated and the application. For example, an antifouling paint having a relatively low viscosity can be used when the fishing net is immersed and processed, or when spray coating is performed.
[0021]
In addition, such an antifouling composition of the present invention can be used effectively for applications in which antifouling treatment is applied to those that are in contact with water for a long period of time, and ships that are in contact with seawater or fresh water, underwater structures. By coating or treating the surface of the body, fishing net or fishing gear with the antifouling paint as described above, good antifouling properties can be imparted to the surface.
The antifouling method of the present invention is a method of coating or treating the surface of an object to be treated such as a ship, underwater structure, fishing net or fishing gear that is in contact with seawater or fresh water with the antifouling paint of the present invention. The method is not particularly limited as long as it is a method capable of imparting antifouling properties to the surface using an antifouling paint. For example, it can be carried out by conventional methods such as coating, adhesion, and immersion.
[0022]
Moreover, the antifouling paint of the present invention contains the antifouling agent composition as described above. Such an antifouling paint can be suitably used for an antifouling treatment that imparts antifouling properties to the surface of an object to be treated such as an underwater structure, a ship, a fishing net, or fishing gear. In addition to the antifouling agent composition as described above, the antifouling paint of the present invention may contain a solvent, a resin, a pigment, and the like as required. For example, when used for ship bottom treatment, A large amount of resin may be contained, and when used for fishing net processing, a large amount of solvent may be contained so that the fishing net can be immersed and processed.
[0023]
The antifouling coating film of the present invention is formed from the antifouling paint as described above. Such an antifouling coating is usually applied to the surface of an object to be treated such as an underwater structure, ship, fishing net or fishing gear in contact with seawater or fresh water, and appropriately dried. It can form by the method of. Further, the antifouling coating film of the present invention may be a film-like material formed by a method such as applying an antifouling paint as described above to the surface of a substance other than the object to be treated, and peeling off after drying. It may be a coating film structure formed by a method such as applying and drying the antifouling paint as described above on the surface of a coating film substrate such as cloth.
[0024]
The antifouling treatment product of the present invention is an antifouling treatment product obtained by coating an underwater structure, a ship, a fishing net or a fishing gear with the antifouling coating film as described above. The antifouling treatment product may be a ship or an underwater structure that is an object to be treated as long as it is partly or entirely covered with the antifouling coating film as described above. It can be formed by a method of forming an antifouling coating film by coating or adhering the antifouling coating film or coating film structure formed in the above-mentioned film shape.
[0025]
【The invention's effect】
According to the present invention, the antifouling agent composition has low toxicity, has an antifouling action over a long period of time, and has an antifouling effect on major aquatic organisms such as barnacles, mussels, selbra, squirts, algae and hydroworms Can be obtained. Further, it is possible to provide an antifouling paint, an antifouling coating film and an antifouling treatment product having good antifouling properties, containing the antifouling agent composition of the present invention, and an effective antifouling method. Can be provided.
[0026]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
[0027]
[Example 1]
SiO 2: 7.7 parts by weight, Al 2 O 3: 0.1 parts by weight, Na 2 O: 5.9 parts by weight, B 2 O 3: 28.8 parts by weight, Cu 2 O: 53.3 parts by weight And the soluble copper glass was prepared with the composition of ZnO: 4.2 weight part. Using this soluble copper glass, raw materials were mixed in the composition shown in Table 1 to prepare an antifouling paint A. The obtained antifouling paint A had good storage stability.
[0028]
Next, the obtained antifouling paint A is applied to a vinyl chloride plate having dimensions of 100 × 300 × 3 mm with an applicator so as to have a dry film thickness of 200 ± 20 μm and dried to have an antifouling coating film. An antifouling treatment product A was prepared.
This antifouling treatment product A was immersed in a water depth of 50 cm off the coast of Miyajima, Hiroshima Prefecture, and the ratio of the aquatic organism adhesion area was investigated every 6 months. The results are shown in Table 2.
[0029]
From Table 2, it can be seen that the antifouling treatment product A has no antifouling property even for a long period of 18 months, and has good antifouling properties over a long period of time. Thus, the antifouling paint A using the antifouling agent composition of the present invention containing (a) soluble copper glass and (b) metal pyrithione has a high antifouling effect over a long period of time. It can be seen that a dirty coating and an antifouling treatment product are obtained.
[0030]
[Example 2]
Using the soluble copper glass prepared in Example 1, raw materials were mixed in the composition shown in Table 1 to prepare an antifouling paint B. The obtained antifouling paint B had good storage stability.
Next, an antifouling product B was prepared in the same manner as in Example 1 except that the antifouling paint B was used, and the proportion of the aquatic organism adhesion area was investigated in the same manner as in Example 1. The results are shown in Table 2.
[0031]
From Table 2, it can be seen that the antifouling treatment product B has good antifouling properties over a long period of time without adhesion of aquatic organisms even for a long period of 18 months. Thus, from the antifouling paint B using the antifouling composition of the present invention containing (a) soluble copper glass, (b) metal pyrithione and (c) a specific organic antifouling agent, It can be seen that an antifouling coating film and an antifouling treatment product having a high antifouling effect over a long period are obtained.
[0032]
[Comparative Examples 1 and 2]
The raw materials were mixed in the composition shown in Table 1 to prepare antifouling paints D and E, respectively.
Next, the antifouling treatment products D and E were respectively prepared in the same manner as in Example 1 except that each prepared antifouling paint was used. Further, in the same manner as in Example 1, the adhesion area of aquatic organisms was adjusted. The proportion was investigated. The results are shown in Table 2.
[0033]
From Table 2, antifouling treatment products D and E show good antifouling properties in the immersion period of 6 months, but adhesion of aquatic organisms is seen in the immersion period of 12 months or more, and the antifouling properties are reduced. I understand that. The aquatic organisms attached at the soaking period of 12 months and 18 months were barnacles, white light boys, sehapura and seaweed.
[0034]
[Table 1]
[Table 2]
[Example 3]
Using the soluble copper glass prepared in Example 1, raw materials were mixed with the compositions shown in Table 3 to prepare antifouling paint C for fishing nets. This antifouling paint C had good storage stability.
Next, a knotless net made of polyethylene (7 nodes, 400 denier, 50) was dip-coated on the obtained antifouling paint C and dried to prepare an antifouling treatment product C.
[0037]
This antifouling treatment product C was immersed in a water depth of 2 m in Sukumo Bay, Kochi Prefecture, for 6 months from March 10 to October 10, 1998, and the state of attachment of aquatic organisms was investigated. The results are shown in Table 4.
From Table 4, the antifouling processed material obtained by processing with the antifouling paint C for fishing nets using the antifouling agent composition of the present invention containing (a) soluble copper glass and (b) metal pyrithione. C (Anti-fouling treated fishing net) has no adhesion to any species of aquatic organisms such as barnacles, sea squirts, hydras, and anti-fouling products with good antifouling properties are obtained. I understand.
[0038]
[Comparative Examples 3 to 5]
The raw materials were mixed in the composition shown in Table 3 to prepare antifouling paints F, G, and H for fishing nets, respectively.
Next, antifouling treatment products F, G, and H were prepared in the same manner as in Example 3 except that the prepared antifouling paints were used. Furthermore, about the obtained antifouling processing thing, it carried out similarly to Example 3, and investigated the adhesion state of the aquatic organism. The results are shown in Table 4.
[0039]
From Table 4, it can be seen that in Comparative Examples 3 and 5, adhesion of all investigated aquatic organisms was observed and the antifouling property was poor. In Comparative Example 4, hydra selectively exhibits antifouling properties, but does not exhibit antifouling properties against other aquatic organisms, and has a selective antifouling effect. It turns out that it is inferior.
[0040]
[Table 3]
[Table 4]
As shown in the above Examples and Comparative Examples, the antifouling composition of the present invention comprising (a) soluble copper glass and (b) metal pyrithione, or (a) soluble copper glass, (b The antifouling composition of the present invention comprising a metal pyrithione and (c) an organic antifouling agent has an antifouling action for a long period of time, and has been used in the main It can be seen that it has an antifouling effect on aquatic organisms.
Claims (9)
（ｂ）銅ピリチオンと、
（ｅ）樹脂成分と、
を含有し、
溶解性銅ガラス（ａ）１００重量部に対して、銅ピリチオン（ｂ）を１〜２００重量部で含むことを特徴とする防汚剤組成物。(A) soluble copper glass;
(B) copper pyrithione ;
(E) a resin component;
Containing
An antifouling composition comprising 1 to 200 parts by weight of copper pyrithione (b) with respect to 100 parts by weight of soluble copper glass (a).
（ｂ）銅ピリチオン、
（ｃ）Ｎ，Ｎ−ジメチルジクロロフェニル尿素、２，４，６−トリクロロフェニルマレイミド、２−メチルチオ−４−ｔｅｒｔ−ブチルアミノ−６−シクロプロピルアミノＳトリアジン、４，５−ジクロロ−２−ｎ−オクチル−イソチアゾリン−３−オンおよび２，４，５，６−テトラクロロイソフタロニトリルからなる群から選ばれる少なくとも１種の有機防汚剤
および
（ｅ）樹脂成分
を含有し、
溶解性銅ガラス（ａ）１００重量部に対して、銅ピリチオン（ｂ）を１〜２００重量部および、有機防汚剤（ｃ）を１〜２００重量部それぞれ含むことを特徴とする防汚剤組成物。(A) soluble copper glass,
(B) copper pyrithione ,
(C) N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino S-triazine, 4,5-dichloro-2-n- Containing at least one organic antifouling agent selected from the group consisting of octyl-isothiazolin-3-one and 2,4,5,6-tetrachloroisophthalonitrile, and (e) a resin component,
Antifouling agent comprising 1 to 200 parts by weight of copper pyrithione (b) and 1 to 200 parts by weight of organic antifouling agent (c) for 100 parts by weight of soluble copper glass (a) Composition.
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| US10314313B2 (en) | 2015-05-05 | 2019-06-11 | Corning Incorporated | Antimicrobial materials exhibiting synergistic efficacy |
| US11884841B2 (en) | 2016-07-19 | 2024-01-30 | Behr Process Corporation | Antimicrobial paint composition and related methods |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10040814A1 (en) * | 2000-08-21 | 2002-03-07 | Thor Gmbh | Synergistic biocide composition |
| JP4812895B1 (en) | 2010-11-10 | 2011-11-09 | 日東化成株式会社 | Antifouling paint composition, fishing net to which the paint composition is applied, fishing net equipment and underwater construction |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62158202A (en) * | 1985-12-28 | 1987-07-14 | Sakai Glass Kk | Antifouling agent |
| JPS6348366A (en) * | 1986-08-18 | 1988-03-01 | Chugoku Toryo Kk | Antifouling paint composition |
| JPH0340936A (en) * | 1989-07-06 | 1991-02-21 | Shinagawa Refract Co Ltd | Thermal spray material for preventing sticking of shellfish and algae and its using method |
| JPH08252533A (en) * | 1995-03-15 | 1996-10-01 | Chugoku Marine Paints Ltd | Stain resistant coating material, coated film formed from this stain resistant coating material and stainproof method using the stain resistant coating material and stain resistant film-coated formed body |
| JPH10298454A (en) * | 1997-04-23 | 1998-11-10 | Nippon Paint Co Ltd | Antifouling coating composition |
| JPH10298455A (en) * | 1997-04-23 | 1998-11-10 | Nippon Paint Co Ltd | Antifouling coating composition |
-
1999
- 1999-03-16 JP JP06948699A patent/JP4601739B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62158202A (en) * | 1985-12-28 | 1987-07-14 | Sakai Glass Kk | Antifouling agent |
| JPS6348366A (en) * | 1986-08-18 | 1988-03-01 | Chugoku Toryo Kk | Antifouling paint composition |
| JPH0340936A (en) * | 1989-07-06 | 1991-02-21 | Shinagawa Refract Co Ltd | Thermal spray material for preventing sticking of shellfish and algae and its using method |
| JPH08252533A (en) * | 1995-03-15 | 1996-10-01 | Chugoku Marine Paints Ltd | Stain resistant coating material, coated film formed from this stain resistant coating material and stainproof method using the stain resistant coating material and stain resistant film-coated formed body |
| JPH10298454A (en) * | 1997-04-23 | 1998-11-10 | Nippon Paint Co Ltd | Antifouling coating composition |
| JPH10298455A (en) * | 1997-04-23 | 1998-11-10 | Nippon Paint Co Ltd | Antifouling coating composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10314313B2 (en) | 2015-05-05 | 2019-06-11 | Corning Incorporated | Antimicrobial materials exhibiting synergistic efficacy |
| US11884841B2 (en) | 2016-07-19 | 2024-01-30 | Behr Process Corporation | Antimicrobial paint composition and related methods |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000264804A (en) | 2000-09-26 |
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