JP2004307764A - Coating material composition, antifouling coating film, underwater structure and method for forming antifouling coating film for underwater structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a coating material composition, to prepare an antifouling coating film, to provide an underwater structure and a method for forming the antifouling coating film on the underwater structure that exhibits excellent marine organism-antifouling effect for a long period of time without film peeling off or cracking with the passage of time to keep the environment safe, since the coating film is consumed slowly at a certain speed after immersed into sea water. <P>SOLUTION: This coating material composition contains at least one kind selected from a specific organic silyl hydrolytic resin and a specific diphenyl borane. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

（一般式（１）中、Ｒ^１〜Ｒ^３はいずれも炭素数１〜２０の炭化水素基であって、互いに同一の基であっても異なる基であってもよい。Ｘは、アクリロイルオキシ基、メタクリロイルオキシ基、マレイノイルオキシ基、フマロイルオキシ基又はイタコノイルオキシ基である。）
【化７】

（一般式（２）中、Ｙは、ハロゲン、炭素数１〜８のアルキル基又は炭素数１〜８のアルコキシ基である。ｎは０〜３の整数である。ｎが２又は３であるとき、Ｙは同一であっても相違していてもよい。Ｒ^４は炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数２〜８のアルケニル基、炭素数２〜８のアルキニル基、ヒドロキシ基、又はハロゲンを示す。
一般式（２）中、Ｒ^５は、以下の一般式（３）、ハロゲンで置換できる５，６，７，８−テトラヒドロイソキノリン基、イソキノリン基、一般式（４）又は一般式（５）のいずれかの基を示す。）
【化８】

（一般式（３）中、Ｚは、ハロゲン、炭素数１〜８のアルキル基、フェニル基又はアセチル基である。ｍは０〜３の整数である）
【化９】

（一般式（４）中、Ｒ^６は炭素数が３〜２４の直鎖又は分岐状のアルキル基を示す。）
【化１０】

（一般式（５）中、Ｒ^７は炭素数が３〜２４の直鎖又は分岐状のアルキル基を示す。Ｒ^８は炭素数３〜２４の直鎖又は分岐状のアルキル基を示す。）
本発明の好適な態様において、前記塗料組成物は、前記樹脂Ｍに対して０．１〜９０質量％の割合でロジン化合物を含有して成り、
本発明の好適な態様において、前記塗料組成物は、海棲生物の付着を阻害する海棲生物付着阻害剤を含有して成り、
本発明の好適な態様において、前記塗料組成物における前記海棲生物付着阻害剤は、金属を含まない有機系阻害剤である。
他の本発明は、本発明に係る前記塗料組成物から形成されて成ることを特徴とする防汚塗膜である。
さらに他の本発明は、海水又は淡水と接触する水中構造物の表面が、前記請求項１〜４のいずれか一項に記載の塗料組成物から形成された防汚塗膜で被覆されて成ることを特徴とする水中構造物である。
その他の本発明は、水中構造物の表面に、前記請求項１〜４のいずれかに記載の塗料組成物を塗布して、防汚塗膜を形成することを特徴とする水中構造物の防汚塗膜形成方法である。
【００２０】
本発明の塗料組成物においては、その必須成分のひとつとして、上記の一般式（１）で表される単量体Ａの一種又は二種以上からなる重合体ＰＡ、及び／又は上記単量体Ａの一種又は二種以上と上記単量体Ａと共重合可能な単量体Ｂの一種又は二種以上との共重合体ＰＡＢを使用する。
【００２１】
単量体Ａは、一般式（１）にて表されるように、分子内に不飽和基（Ｘ）として、アクリロイルオキシ基、メタクリロイルオキシ基、マレイノイルオキシ基〔主にモノアルキル（炭素数１〜６）エステルマレイノイルオキシ基〕、フマロイルオキシ基〔主にモノアルキル（炭素数１〜６）エステルフマロイルオキシ基〕、又はイタコノイルオキシ基〔主にモノアルキル（炭素数１〜６）エステルイタコノイルオキシ基〕を有するとともに、トリオルガノシリル基を有するものである。
【００２２】
トリオルガノシリル基において、３個の炭化水素基（Ｒ^１ 〜Ｒ^３ ）は、同一の基であっても異なる基であってもよい。具体的には、メチル、エチル、プロピル、ブチルなどの炭素数が２０以下である、直鎖状又は分岐状である、無置換アルキル基及び置換アルキル基；シクロプロピル、シクロヘキシルなどの、置換基を有してもよい環状アルキル基；フェニル基のような、置換基を有してもよいアリール基；並びに、ナフチル基のような、置換基を有してもよい多環式アリール基などがある。
【００２３】
また、置換アルキル基の置換基としては、ハロゲン、アリール基、アシル基、アルコキシ基、アリロキシ基、ニトロ基及びアミノ基などが、また置換アリール基の置換基としては、ハロゲン、アルキル基、アシル基、アルコキシ基、アリロキシ基、ニトロ基及びアミノ基などが、それぞれ挙げられる。
【００２４】
このような単量体Ａとしては、分子内に（メタ）アクリロイルオキシ基を有するものとして、トリメチルシリル（メタ）アクリレート、トリエチルシリル（メタ）アクリレート、トリｎ−プロピルシリル（メタ）アクリレート、トリｉ−プロピルシリル（メタ）アクリレート、トリｎ−ブチルシリル（メタ）アクリレート、トリｉ−ブチルシリル（メタ）アクリレート、トリｓ−ブチルシリル（メタ）アクリレート、トリｎ−アミルシリル（メタ）アクリレート、トリｉ−アミルシリル（メタ）アクリレート、トリｎ−ヘキシルシリル（メタ）アクリレート、トリｎ−オクチルシリル（メタ）アクリレート、トリｎ−ドデシルシリル（メタ）アクリレート、トリｎ−イコサシリル（メタ）アクリレート、トリフェニルシリル（メタ）アクリレート、トリｐ−メチルフェニルシリル（メタ）アクリレート、トリベンジルシリル（メタ）アクリレート、トリ２−メトキシエチルシリル（メタ）アクリレートなどが挙げられる。
【００２５】
また、分子内に（メタ）アクリロイルオキシ基を有する他の例として、エチルジメチルシリル（メタ）アクリレート、ジメチルｎ−プロピルシリル（メタ）アクリレート、ジメチルｉ−プロピルシリル（メタ）アクリレート、ｎ−ブチルジメチルシリル（メタ）アクリレート、ｓ−ブチルジメチルシリル（メタ）アクリレート、ｉ−ブチルジメチルシリル（メタ）アクリレート、ｔ−ブチルジメチルシリル（メタ）アクリレート、ｎ−アミルジメチルシリル（メタ）アクリレート、ｉ−アミルジメチルシリル（メタ）アクリレート、ｎ−イコシルジメチルシリル（メタ）アクリレート、ｎ−オクチルジｎ−ブチルシリル（メタ）アクリレート、ジｉ−プロピルステアリルシリル（メタ）アクリレート、ジシクロヘキシルフェニルシリル（メタ）アクリレート、ラウリルジフェニルシリル（メタ）アクリレート、エチルジｎ−オクチルシリル（メタ）アクリレート、ｔ−ブチルジフェニルシリル（メタ）アクリレート、シクロヘキシルジ−ｐ−トリルシリル（メタ）アクリレート、ジｔ−ブチルメチルシリル（メタ）アクリレート、ｎ−イコサ−ジｏ−ニトロフェニルシリル（メタ）アクリレート、ｉ−アミルジｍ−クロロフェニルシリル（メタ）アクリレート、エチルメチルｎ−プロピルシリル（メタ）アクリレート、ｉ−アミルｔ−ブチルメチルシリル（メタ）アクリレート、ｏ−シアノフェニルシクロヘキシルナフチルシリル（メタ）アクリレートなどが挙げられる。
【００２６】
分子内にマレイノイルオキシ基を有するものとして、トリメチルシリルメチルマレート、トリエチルシリルｎ−プロピルマレート、トリｉ−プロピルシリルメチルマレート、トリｉ−プロピルシリルｎ−アミルマレート、トリｎ−プロピルシリルｎ−アミルマレート、トリｉ−プロピルシリルｉ−アミルマレート、トリｎ−ブチルシリルｎ−ブチルマレート、ｔ−ブチルジフェルシリルメチルマレート、ｔ−ブチルジフェニルシリルｎ−ブチルマレート、トリｎ−ブチルシリル２−エチルヘキシルマレート、トリｓ−ブチルシリルｎ−オクチルマレート、トリｎ−アミルシリルフェニルマレート、トリｉ−アミルシリルベンジルマレート、トリｎ−ドデシルシリルｏ−ニトロフェニルマレート、トリｎ−イコシルシリルｐ−トリルマレート、トリフェニルシリル２−メトキシエチルマレート、トリベンジルシリルｍ−ブロモフェニルマレート、トリ２−メトキシエチルシリルシクロヘキシルマレート、エチルジメチルシリルメチルマレート、ジメチルｎ−プロピルシリルメチルマレート、ジメチルｉ−プロピルシリルｎ−アミルマレート、ｎ−ブチルジメチルシリルｉ−アミルマレート、ｓ−ブチルジメチルシリルフェニルマレート、ｉ−ブチルジメチルシリルシクロヘキシルマレート、ｔ−ブチルジメチルシリルｏ−Ｎ，Ｎ−ジメチルアミノフエニルマレート、ｎ−アミルジメチルシリルｔ−ブチルマレート、ｉ−アミルジメチルシリル２−メトキシエチルマレート、ｎ−イコサジメチルシリル２−エトキシエチルマレート、エチルジ−ｎ−オクチルシリルｐ−トリルマレート、ｔ−ブチルジフェニルシリル３−メトキシシクロヘキシルマレート、ジｔ−ブチルメチルシリルｉ−プロピルマレート、ｎ−イコサ−ジｏ−ニトロフェニルシリルｍ−フルオロフェニルマレート、ｉ−アミルジｍ−クロロフェニルシリル２−エチルヘキシルマレート、エチルメチルｎ−プロピルシリルｉ−ブチルマレート、ｉ−アミルｔ−ブチルメチルシリルｓ−ブチルマレート、ｏ−シアノフェニルシクロヘキシルナフチルシリルメチルマレートなどが挙げられる。これらの中でも炭素数が１〜６であるアルキル基を有するモノアルキルエステルマレイノイルオキシ基を置換したオルガノシランが好ましい。
【００２７】
分子内にフマロイルオキシ基を有するものとして、メチルトリメチルシリルフマレート、トリｉ−プロピルシリルメチルフマレート、トリｉ−プロピルシリルｎ−アミルフマレート、ジトリエチルシリルフマレート、トリｎ−プロピルシリルｎ−アミルフマレート、トリｉ−プロピルシリルｉ−アミルフマレート、トリｎ−ブチルシリル２−エチルヘキシルフマレート、トリｎ−ブチルシリルｎ−ブチルフマレート、ｔ−ブチルジフェニルシリルメチルフマレート、トリｓ−ブチルシリルｎ−オクチルフマレート、トリｉ−ブチルシリルｎ−ブチルフマレート、ｔ−ブチルジフェニルシリルｎ−ブチルフマレート、トリｎ−アミルシリルフェニルフマレート、トリｉ−アミルシリルベンジルフマレート、トリｎ−ドデシルシリルｏ−ニトロフェニルフマレート、トリｎ−イコサシリルｐ−トリルフマレート、トリフェニルシリル２−メトキシエチルフマレート、トリベンジルシリルｍ−ブロモフェニルフマレート、トリ２−メトキシエチルシリルシクロヘキシルフマレート、エチルジメチルシリルメチルフマレート、エチルジメチルｎ−プロピルシリルフマレート、ジメチルｉ−プロピルシリルｎ−アミルフマレート、ｎ−ブチルジメチルシリルｉ−アミルフマレート、ｓ−ブチルジメチルシリルフェニルフマレート、ｉ−ブチルジメチルシリルシクロヘキシルフマレート、ｔ−ブチルジメチルシリルｏ−Ｎ，Ｎ−ジメチルアミノフェニルフマレート、ｎ−アミルジメチルシリルｔ−ブチルフマレート、ｉ−アミルジメチルシリル２−メトキシエチルフマレート、ｎ−イコサジメチルシリル２−エトキシエチルフマレート、エチルジｎ−オクチルシリルｐ−トリルフマレート、ｔ−ブチルジフェニルシリル３−メトキシシクロヘキシルフマレート、ベンジルシクロヘキシルジｐ−トリルシリルフマレート、ジｔ−ブチルメチルｉ−プロピルフマレート、ｎ−イコサ−ジｏ−ニトロフェニルシリルｍ−フルオロフェニルフマレート、ｉ−アミルジｍ−クロロフェニルシリル２−エチルヘキシルフマレート、エチルメチルｎ−プロピルシリルｉ−ブチルフマレート、ｉ−アミルｔ−ブチルメチルシリルｓ−ブチルフマレート、ｏ−シアノフェニルシクロヘキシルナフチルシリルメチルフマレートなどが挙げられる。これらの中でも炭素数が１〜６であるアルキル基を有するモノアルキルエステルフマノイルオキシ基を置換したオルガノシランが好ましい。
【００２８】
分子内にイタコノイルオキシ基を有するものとして、トリメチルシリルメチルイタコネート、トリエチルシリルｎ−プロピルイタコネート、トリｎ−プロピルシリルｎ−アミルイタコネート、トリｉ−プロピルシリルｉ−アミルイタコネート、トリｎ−ブチルシリル２−エチルヘキシルイタコネート、トリｓ−ブチルシリルｎ−オクチルイタコネート、トリｎ−アミルシリルフェニルイタコネート、トリｉ−アミルシリルベンジルイタコネート、トリｎ−ドデシルシリルｏ−ニトロフェニルイタコネート、トリｎ−イコサシリルｐ−トリルイタコネート、トリフェニルシリル２−メトキシエチルイタコネート、トリベンジルシリルｍ−ブロモフェニルイタコネート、トリ２−メトキシエチルシリルシクロヘキシルイタコネート、エチルジメチルシリルメチルイタコネート、ジメチルｎ−プロピルシリルメチルイタコネート、ジメチルｉ−プロピルシリルｎ−アミルイタコネート、ｎ−ブチルジメチルシリルｉ−アミルイタコネート、ｓ−ブチルジメチルシリルフェニルイタコネート、ｉ−ブチルジメチルシリルシクロヘキシルイタコネート、ｔ−ブチルジメチルシリルｏ−Ｎ，Ｎ−ジメチルアミノフェニルイタコネート、ｎ−アミルジメチルシリルｔ−ブチルイタコネート、ｉ−アミルジメチルシリル２−メトキシエチルイタコネート、ｎ−イコシルジメチルシリル２−エトキシエチルイタコネート、エチルジｎ−オクチルシリルｐ−トリルイタコネート、ｔ−ブチルジフェニルシリル３−メトキシシクロヘキシルイタコネート、ジｔ−ブチルメチルｉ−プロピルイタコネート、ｎ−イコサ−ジｏ−ニトロフェニルシリルｍ−フルオロフェニルイタコネート、ｉ−アミルジｍ−クロロフェニルシリル２−エチルヘキシルイタコネート、エチルメチルｎ−プロピルシリルｉ−ブチルイタコネート、ｉ−アミルｔ−ブチルメチルシリルｓ−ブチルイタコネート、ｏ−シアノフェニルシクロヘキシルナフチルシリルメチルイタコネートなどが挙げられる。これらの中でも炭素数が１〜６であるアルキル基を有するモノアルキルエステルイタコノイルオキシ基を置換したオルガノシランが好ましい。
【００２９】
これらの単量体Ａと共重合可能な他の単量体Ｂとしては、たとえば、アクリル酸エステル、メタクリル酸エステル、スチレン、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、及び安息香酸ビニルなどのビニルエステル類、並びにビニルトルエン、α−メチルスチレン、クロトン酸エステル類、及びイタコン酸エステル類などの各種のビニル系単量体を使用することができる。
【００３０】
本発明における樹脂Ｍは、様々な態様を有し、例えば前記単量体Ａの一種を重合して成る単独重合体、前記単量体Ａの二種以上を共重合して成る共重合体、前記単量体Ａと共重合可能な前記単量体Ａ以外の単量体Ｂの一種又は二種以上と単量体Ａの一種又は二種以上との単量体混合物を重合して成る共重合体、及びこれら重合体の混合物からなる樹脂を挙げることができる。
前記単量体Ａの二種以上を共重合して成る共重合体における単量体Ａと他の単量体Ａとのモノマー比について、特に制限はない。
前記単量体混合物において、単量体Ａ及びこれらと共重合可能な他の単量体Ｂの使用割合は、塗料組成物の使用目的に応じて適宜設定できるが、一般には、単量体Ａが１〜９５質量％、これらと共重合可能な他の単量体Ｂが５〜９９質量％となるようにするのがよい。
【００３１】
前記重合体ＰＡ又は共重合体ＰＡＢは、ビニル重合開始剤の存在下、公知の重合方法、たとえば溶液重合、塊状重合、乳化重合、懸濁重合などの各種方法で重合させることにより、得ることができる。前記重合体ＰＡ及び／又は共重合体からなる樹脂Ｍを塗料用とする際、有機溶剤で希釈して適当な粘度の樹脂溶液とするのが好都合であり、そのためには、溶液重合法又は塊状重合法を採用するのが望ましい。
【００３２】
上記のビニル重合開始剤としては、通常の重合で使用される開始剤を重合法に合わせて選択し、使用することができる。具体例としては、２，２’−アゾビス−イソブチロニトリル、２，２’−アゾビス−２−メチルブチロニトリル、２，２’−アゾビス−２，４−ジメチルバレーロニトリル、１，１’−アゾビス−１−シクロヘキサンカルボニトリル、ジメチル−２，２’−アゾビスイソブチレート、４，４’−アゾビス−４−シアノバレーリツク酸、２，２’−アゾビス−（２−アミジノプロパン）ジハイドロクロライドなどのアゾビス系開始剤、ベンゾイルパーオキサイド、ｔ−ブチルパーオキシ（２−エチルヘキサノエート）、ｔ−ブチルパーオキシイソプロピルカーボネート、ｔ−ブチルパーオキシベンゾエートなどの過酸化物系開始剤などが挙げられる。
【００３３】
また、上記の有機溶剤としては、種々の有機溶剤の中から、単量体の種類や重合温度によって選択し、一種又は二種以上を混合して使用することができる。具体的には、ペンタン、ヘキサン、ヘプタンなどの脂肪族炭化水素系溶剤、ベンゼン、トルエン、キシレンなどの芳香族炭化水素系溶剤、酢酸エチル、酢酸ブチル、酢酸イソブチルなどのエステル系溶剤、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン系溶剤、エタノール、イソプロパノール、ブタノールなどのアルコール系溶剤などが挙げられる。
【００３４】
このような方法で得られる前記重合体ＰＡ及び前記共重合体ＰＡＢそれぞれの分子量は、重量平均で１，０００〜３００，０００の範囲にあるのが望ましい。分子量が低すぎると、正常な塗膜の形成が難しく、また高すぎると、塗膜時に多くのシンナーを必要とするため、必要濃厚を得るために多くの塗装回数を要するという不具合が出てくる。また、この樹脂溶液の粘度は、２５℃で１５０ポイズ以下であるのが好都合であり、そのためには、樹脂溶液の固型分は５〜９０質量％、好ましくは１５〜８５質量％の範囲となるようにするのがよい。
【００３５】
本発明の塗料組成物は、樹脂成分として、上記の方法で得られる重合体ＰＡ及び／又は共重合体ＰＡＢを用いることを必須成分とするが、本発明の効果を妨げない限り、上記以外の他の重合体を少量併用してもよい。
【００３６】
本発明に係る塗料組成物においては、前記樹脂Ｍとともにロジン化合物を使用してもよい。ここで、ロジン化合物としては、ロジン、ロジン誘導体又はロジン金属塩等を挙げることができる。たとえば、ロジンとしてはトールロジン、ガムロジン、ウッドロジンなどが、ロジン誘導体としては、水添ロジン、ロジンと無水マレン酸を反応させたマレン化ロジン、ホルミル化ロジン、重合ロジンなどが、ロジン金属塩としては、ジンクロジネート、カルシウムロジネート、カッパーロジネート、マグネシウムロジネート、その他金属化合物とロジンとの反応物などが挙げられる。
【００３７】
本発明においては、このようなロジン化合物の中から一種又は二種以上を選択して使用するが、使用量は、このロジン化合物を上記樹脂Ｍに対して、固形分比率で、０．１〜９０質量％、好ましくは、０．１〜８０質量％となるようにするのがよい。
【００３８】
ロジン化合物が過多となると塗膜形成能が低下して塗膜にクラック、及び剥離などの欠陥が生じやすく、効果的な海棲生物付着防止性能が得られにくい。過少の場合には、ロジン化合物の有効性が発揮されない。
【００３９】
本発明における樹脂Ｍは、前記重合体ＰＡ及び／又は前記共重合体ＰＡＢから成る限りでは樹脂Ｍ中に金属を含有することがないのであるが、また樹脂Ｍ中に金属を含有しないという条件を満たし、かつ本発明の目的を阻害しない限りにおいて、金属を含有しないその他の重合体及び／又は共重合体を含有することを許容し、さらにまた、本発明の目的特に環境安全性を阻害しない限りにおいて、金属を含有するその他公知の加水分解性樹脂から選ばれる一種又は二種以上を含有することを許容する。前記加水分解性樹脂としては、
下記一般式（６）；
【化１１】

（ただし、一般式（６）において、Ｒ^９は、水素原子又はメチル基、Ｍ^１は、Ｍｇ、Ｚｎ又はＣｕ、Ｒ^１０は、オレン酸、エライジン酸、リノール酸、リノレン酸、ステアリン酸、リシノール酸、リシノエラジン酸、ブラシジン酸、及びエルカ酸から選ばれる、不飽和基を有する有機酸残基を示す。）で示される金属含有重合性単量体を含む単量体混合物を重合してなる加水分解樹脂、又は、前記加水分解樹脂若しくは他の公知の加水分解樹脂の側鎖末端に、
下記一般式（７）；
【化１２】

（ただし、一般式（７）において、ｍは、０、１又は２であり、ｎは、［（金属原子価数）−１］である。Ｍ^２は、Ｓｉ、Ｃｕ又はＺｎを表し、Ｌは、アルキル基、Ｏ（Ｏ＝）Ｃ−Ｒ^１１で表される基、又は、−Ｒ^１２−ＣＯ−ＣＨ_２−ＣＯ−Ｒ^１３で表される基を示す。Ｒ^１１は、炭素数１０以上の炭化水素基を表し、Ｒ^１２は、アルキレン基又はフェニル誘導体からなる２価の基を表し、Ｒ^１３は、アルキル基又はフェニル誘導体からなる１価の基を表す。）を含む加水分解性樹脂、
又は、下記一般式（８）；
【化１３】

（ただし、一般式（８）において、Ｒｐは、基体樹脂を、Ｍ^３は２価の金属原子をそれぞれ表す。）
で示される金属含有加水分解性樹脂などがある。
【００４０】
本発明において、このような公知の加水分解性樹脂の使用量は、上記一般式（１）で表されるシリル基含有共重合体に対して、固形分比率で０．１〜９０質量％、好ましくは、０．１〜８０質量％となるようにするのが良い。
【００４１】
併用する加水分解性樹脂が過多となると、樹脂同士が互いに相溶せず、塗膜形成能が低下し塗膜にクラック、剥離などの欠陥が生じやすく、効果的な海棲生物付着防止性能が得られにくい。過少の場合には、加水分解性樹脂の有効性が発揮されない。
【００４２】
さらに、本発明の塗料組成物は、上記一般式（２）で表される一種以上から選ばれるボラン化合物を必須成分として使用する。上記一般式（２）で表される一種以上から選ばれるボラン化合物として、例えば４−イソプロピルピリジル−ジフェニルメチルボラン、４−フェニルピリジル−ジフェニルボラン、及びジフェニルボラン−ｎ−オクタデシルアミン等を挙げることができる。このようなボラン化合物の使用量は、塗料組成物における固形分中、通常０．０１〜６０質量％、好ましくは０．１〜４０質量％の範囲がよい。
【００４３】
このボラン化合物の使用量が、過少では海棲生物付着阻害効果を期待できず、過多となると塗膜にクラック，剥離などの欠陥が生じやすくなり、やはり良好な阻害効果が得られない。
【００４４】
また、本発明においては、必要により、一般式（２）で表される一種以上から選ばれるボラン化合物以外に、塗料業界で公知の他の海棲生物付着阻害剤を併用することもできる。
【００４５】
この他の海棲生物付着阻害剤は、金属を含まない有機系阻害剤で構成されており、このような有機系阻害剤としては、たとえば、Ｎ−トリハロメチルチオフタルイミド、ジチオカルバミン酸、Ｎ−アリールマレイミド、３−置換アミノ−１，３−チアゾリジン−２，４−ジオン、ジチオシアノ系化合物、トリアジン系化合物、チオシアン酸銅、ピリチオン系化合物及びその他のものがある。
【００４６】
具体的には、２−メチルチオ−４−ｔ−ブチルアミノ−６−シクロプロピルアミノ−ｓ−トリアジン、２，４，５，６−テトラクロロイソフタロニトリル、Ｎ，Ｎ−ジメチル−Ｎ’−ジクロロフェニル尿素、４，５−ジクロロ−Ｎ−オクチル−イソチアゾリン−３−オン、Ｎ−（フルオロジクロロメチルチオ）フタルイミド、Ｎ，Ｎ−ジメチル−Ｎ’−フエニル−Ｎ’−フルオロジクロロメチルチオスルフアミド、テトラメチルチウラムジサルフアイド、２，４，６−トリクロロフエニルマレイミド、２，３，５，６−テトラクロロ−４−（メチルスルホニル）ピリジン、ジヨードメチルパラトリルスルホン、２−（４−チアゾリル）ベンゾイミダゾール、２−ピリジンチオール−１−オキシド亜鉛塩又は銅塩などがある。
【００４７】
さらに、金属を含まない樹脂Ｍと金属を含まない有機系阻害剤を組み合わせることで、環境安全上、金属を含まない加水分解性樹脂と金属を含まない海棲生物付着阻害剤とで形成されてなる塗料組成物が可能となる。
【００４８】
ここで、“金属を含まない”とは、有機系阻害剤（有機化合物）の構成元素のひとつとして銅、錫、水銀などの環境安全性に問題のある金属元素を含まないことを意味し、有機系阻害剤の合成原料に由来する不純物としてのごく微量の上記金属までをも含まないという意味ではない。
【００４９】
本発明の塗料組成物には、溶解速度を調整する目的で、シリコーンオイル、流動パラフィンなどのオイル成分を必要に応じて添加できる。具体的には、オイル成分として、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、ポリエーテル変性シリコーンオイル、ペトロラタム、ポリブテンなどが挙げられる。
【００５０】
本発明の塗料組成物には、その他、本発明の目的を阻害しない限りで、通常の塗料に用いられる弁柄、二酸化チタン、酸化亜鉛、タルクなどの顔料や染料などの着色剤、塗料で常用されているタレ止め剤、色分かれ防止剤、沈降防止剤、消泡剤など、また、可塑剤、その他の樹脂、溶剤などを、必要に応じて配合することができる。上記の可塑剤としては、塩素化パラフィン、ジアルキルフタレート、トリクレジルフォスフェート、トリフェニルフォスフェートなどがある。
【００５１】
本発明の塗料組成物は、従来から知られている塗料の製造方法を用いて製造することができ、塗装方法も、スプレー塗装、ハケ塗り、ローラー塗装、浸漬などの手段を用いて塗装することができる。
本発明の塗料組成物を塗装する表面は、水中構造物における少なくとも喫水表面である。水中構造物としては、船舶、ブイ、定置養魚網、養殖養魚網、各種水管、汚濁防止膜、海底油田掘削井、橋脚、パイプライン、海中ケーブル、熱交換機、ダム、吸水スクリーン等を挙げることができる。
【００５２】
本発明の塗料組成物は、側鎖にトリオルガノシリル基を有する特定の加水分解性樹脂と上記一般式（２）で表される一種以上から選ばれるボラン化合物とを必須成分とすることを特徴としており、それからなる複合材料である防汚塗膜は、全体として海水又は淡水との親和性が防汚塗膜の消耗性に対して非常に良好に設計されていることから、長期に渡って非常に優れた付着阻害性能を発揮する。
【００５３】
また、本発明の塗料組成物は、ハガレ、クラックなどの塗膜欠陥がないばかりでなく、一定で良好な速度で消耗し、自己研磨型塗料であるため塗膜表面に樹脂残査層を形成せず、従来の非加水分解型塗料と比較して、非常に良好なリコート性を示すものである。さらに、他の金属含有海棲生物付着阻害剤を併用しない場合、アルミニウムへの孔食の危険性がない。
【００５４】
また、本発明に係る防汚塗膜は良好な溶解性を有するので、防汚塗膜表面を常に平滑に保つことができる。このため、船舶などの燃費を低減することができ、ひいては二酸化炭素による地球温暖化防止にも貢献できる。さらに、本発明の塗料組成物においては、亜酸化銅を併用しなくても良好な海棲生物付着阻害効果を発揮することができるため、通常の海棲生物付着阻害用の塗料では亜酸化銅などを使用するため鮮明色に着色できないのに対し、どのような鮮明な色にも着色可能であり、意匠性にも優れた塗料組成物である。
【００５５】
【実施例】
つぎに、本発明を製造例、実施例及び比較例によって具体的に説明する。なお、例中の部は、質量部であり、分子量は、ＧＰＣによるポリスチレン換算重量平均分子量である。
【００５６】
また、製造例で用いた単量体Ａ（Ａ１〜Ａ８）は、上記一般式（１）で示される単量体であり、一般式（１）中のＲ^１〜Ｒ^３及びＸは、つぎの表１に示すとおりである。
【００５７】
【表１】

【００５８】
［製造例１〜５］
攪拌機付きのフラスコに、つぎの表２の配合に準じて溶剤ａを仕込み、所定の反応温度に昇温させ、攪拌しながら、単量体Ａとその他の単量体Ｂと重合触媒ａとの混合液をフラスコの中へ３時間で滴下し、滴下終了後同温度で３０分間保持した。ついで、溶剤ｂと重合触媒ｂとの混合物を２０分間で滴下し、さらに同温度で２時間攪拌を続けて重合反応を完結させた。最後に、希釈溶剤を加えて希釈し、各樹脂溶液Ｓ_１〜Ｓ_５を得た。なお、表２において、重合触媒としての「パーブチルＩ」（日本油脂（株）製の商品名）は、ｔ−ブチルペルオキシイソプロピルカーボネートであり、また、「ベオバ９」は（昭和シェル化学（株）製の商品名）ビニルエステル系単量体である。
【００５９】
［製造例６］
攪拌機付きのフラスコに、つぎの表２の配合に準じて、溶剤ａと単量体Ａとその他の単量体Ｂと重合触媒ａとを仕込み、攪拌しながら所定の反応温度に昇温させ、同温度で６時間攪拌を続けて反応を完結させた。つぎに、希釈溶剤で希釈して、樹脂溶液Ｓ_６を得た。
【００６０】
［製造例７］
耐熱耐圧の容器中に、つぎの表２の配合に準じて、単量体Ａとその他の単量体Ｂと重合触媒ａとを仕込み、完全に密封して振蕩しながら所定の反応温度に昇温させ、同温度で８時間振蕩を続けて反応を完結させた。つぎに、希釈溶剤を加えて８時間振蕩して溶解し、樹脂溶液Ｓ_７を得た。
【００６１】
【表２】

【００６２】
［実施例１〜２４］
樹脂溶液Ｓ_１〜Ｓ_７を用いて、つぎの表３〜表５に示す配合組成（表中の数値は、質量％）により、各成分を混合し、２，０００ｒｐｍのホモミキサーで混合分散して、２０種の塗料組成物を得た。なお、各表中、「ＴＳＦ−４４４５」〔東芝シリコーン（株）製商品名〕は、ポリエーテル変性シリコーンオイルであり、「ディスパロンＡ６３０−２０ＸＮ」〔楠本化成（株）製の商品名〕及び「ベントンＳＤ−２」〔ナショナルレッド（株）製の商品名〕は、いずれもタレ止め用添加剤である。また、表５中の「樹脂Ａ」、「樹脂Ｂ」及び「樹脂Ｃ」は下記の通り作製した。なお、各表中の生物付着阻害剤とは、上記一般式（２）で示される化合物に係るものである。
【００６３】
［「樹脂Ａ」の製造手順］
冷却器、温度計、滴下ロート及び攪拌機を備えた四つ口フラスコにプロピレングリコールメチルエーテル２０部及びキシレン４０部を仕込み、攪拌しながら１００℃に昇温した。次に、滴下ロートからプロピレングリコールメチルエーテル１０部及びキシレン１０部とオレン酸亜鉛メタクリレート３０部、メチルメタクリレート５部、エチルアクリレート６０部、ｔ−ブチルパーオクトレート１．５部を混合した混合物を４時間で等速滴下した。滴下終了後にｔ−ブチルパーオクトレート１部とキシレン１０部を１時間で滴下し、さらに２時間攪拌した後キシレン１０添加して「樹脂Ａ」を得た。
【００６４】
［「樹脂Ｂ」の製造手順］
冷却器、温度計、滴下ロート及び攪拌機を備えた四つ口フラスコに、キシレン３０部、ｎ−ブタノール１５部を仕込み、攪拌しながら１１０℃に昇温した。次に、アクリル酸７．２部、メチルメタクリレート４．５部、エチルアクリレート３８．３部及びアゾビスイソブチロニトリル１部を混合した混合物を４時間で等間隔に滴下した。滴下終了後にｔ−ブチルパーオキシ２−エチルヘキサノエート０．３部及びキシレン５部の混合物を１時間で滴下し、さらに３時間攪拌し、樹脂溶液を得た。この樹脂溶液１００部に酢酸銅１０部及びオレン酸５．６部を加え、還流下で生成する水を除去しながら、６時間反応させ、キシレン６．３部を加えて冷却し、「樹脂Ｂ」を得た。
【００６５】
［「樹脂Ｃ」の製造手順］
冷却器、温度計、滴下ロート及び攪拌機を備えた四つ口フラスコに、キシレン２３部、酢酸ブチル３０部、ｎ−ブタノール３０部を仕込み、攪拌しながら１０５℃に昇温した。次に、メタクリル酸１５部、メトキシエチルアクリレート４０部、メチルメタクリレート５部及びアゾビスイソブチロニトリル８部を混合した混合物を４時間で等速滴下した。滴下終了後にキシレン６部及びアゾビスイソブチロニトリル１部の混合物を１時間で滴下し、さらに１時間攪拌し、樹脂溶液を得た。この樹脂溶液１００部に、酸化亜鉛７．５部、水５．３部、酢酸ブチル７．５部及びｎ−ブタノール７．５部を加え、１００℃で２０時間攪拌し、「樹脂Ｃ」を得た。
【００６６】
【表３】

【００６７】
【表４】

【００６８】
【表５】

【００６９】
［比較例１〜５］
重合体溶液Ｓ１〜Ｓ５を用い、つぎの表６に示す配合組成（表中の数値は質量％）により、各成分を混合し、２，０００ｒｐｍのホモミキサーで混合分散して、３種の塗料組成物を調製した。なお、表５中、「ＴＳＦ−４４４５」、「ディスパロンＡ６３０−２０ＸＮ」及び「ベントンＳＤ−２」は、前記の表２〜表３の場合と同じである。
【００７０】
【表６】

【００７１】
以上の実施例１〜３４および比較例１〜７の各塗料組成物について、下記の要領により、塗膜消耗試験、海棲生物付着阻害試験、付着性試験および耐クラック性試験を行った。
【００７２】
［塗膜消耗試験］
調製後５０℃のオーブンに入れて２週間保存した各塗料組成物を、裏面に防錆塗装をした鋼板（１００ｍｍ×１００ｍｍ×１ｍｍ）のおもて面に、乾燥膜厚が３００μｍとなるようにスプレー塗装し、温度２０℃の室内にて１週間乾燥させて、試験片を作製した。直径５０ｃｍの円筒形ドラムの外面に、上記の試験片を固定したのち、兵庫県洲本市由良湾の海面下１ｍに浸漬して、ドラムの周速が１６ノツトとなるようにモータで回転させ、消耗した塗膜厚を３ケ月毎に１２ケ月間測定した。また、塗膜厚消耗平均速度（μｍ／月）を算出した。なお、塗膜厚消耗平均速度は、３μｍ／月以上であれば良好な防汚性能と相関する。
【００７３】
［海棲生物付着阻害試験］
ブラスト鋼板（１００ｍｍ×３００ｍｍ×１ｍｍ）の両面にタールエポキシ系防錆塗料を１回あたり１２５μｍの乾燥膜厚となるようにスプレー塗装で２回塗りし、さらにビニル系シーラーコートを乾燥膜厚が５０μｍとなるように塗装した。この両面に、各塗料組成物を、乾燥膜厚が片面１５０μｍとなるようにスプレー塗りにより塗装して、温度２０℃，湿度６５％の恒温恒湿室にて１週間乾燥させ、試験片を作製した。この試験片につき、大阪府高石市の大阪湾内にて、１２ケ月の海水浸漬を行い、試験塗膜上の付着生物の占有面積（付着面積）の割合を経時的に測定した。
【００７４】
［付着性試験］
ブラスト鋼板（１００ｍｍ×３００ｍｍ×１ｍｍ）の両面にタールエポキシ系防錆塗料を１回あたり１２５μｍの乾燥膜厚となるようにスプレー塗装で２回塗りし、さらにビニル系シーラーコートを乾燥膜厚が５０μｍとなるように塗装した。この上に、各塗料組成物を、乾燥膜厚が１５０μｍとなるようにスプレー塗りにより塗装して、温度２０℃，湿度６５％の恒温恒湿室にて１週間乾燥させ、試験片を作製した。この試験片を人工海水に浸漬し、３ケ月後、６ケ月後、９ケ月後、および１２ケ月後に引き上げて、２ｍｍ間隔のゴバン目試験を実施した。密着性の評価は、この試験による剥離個数が２５個／２５個の場合を○（合格）、同剥離個数が２４個以下／２５個の場合を×（不合格）とした。
【００７５】
［耐クラック性試験］
密着性試験において、試験片を人工海水から引き上げる際に、その塗膜を目視観察し、クラックの発生の有無を調べた。クラックのないものを○（合格）、あるものを×（不合格）とした。
【００７６】
【表７】

【００７７】
【表８】

【００７８】
【表９】

【００７９】
【表１０】

【００８０】
【表１１】

【００８１】
上記の表６〜表１１の結果から明らかなように、比較例１〜７の各塗料組成物では、比較例１〜７に見られるように塗膜消耗速度、海棲生物付着阻害性能、塗膜物性ともに不満足な結果であったが、本発明の実施例１〜３４の各塗料組成物では、いずれの試験においても満足できる結果を示しており、これらの結果からも、本発明の塗料組成物は、有機シリル系加水分解性樹脂と海棲生物付着阻害剤とからなる、環境安全性に非常に優れ、良好な性能を具備しているものであることがわかった。
【００８２】
【発明の効果】
本発明によれば、海水又は淡水に浸漬した後においても、経時的にハガレやクラックなどの塗膜欠陥を生じず、一定速度で消耗し、長期に渡って良好な海棲生物付着阻害効果を発揮する環境安全性に非常に優れた塗料組成物、防汚塗膜、水中構造物、及び水中構造物の防汚塗膜形成方法を提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a coating composition, an antifouling coating film, an underwater structure, and a method for forming an antifouling coating film on an underwater structure, and more particularly, to a ship, buoy, stationary fishnet, cultured fishnet, various water pipes, pollution Coating compositions used to prevent marine organisms from adhering to underwater structures having sites that come in contact with seawater or freshwater, such as barrier coatings, submerged parts such as offshore oil drilling wells, and such coatings An antifouling coating formed using the composition, an underwater structure obtained by forming such an antifouling coating on a contact surface of seawater or fresh water, and an antifouling coating formed on the surface of the underwater structure. The present invention relates to a method for forming a dirty coating film.
[0002]
[Prior art]
Conventionally, barnacles, mussels, mosquitoes, sea squirts on underwater structures that come in contact with seawater or freshwater, such as submerged parts such as ships, buoys, fixed fish nets, cultured fish nets, various water pipes, pollution control membranes, submersible oil field drilling wells, etc. Contains mainly organic tin-based hydrolysis resin and inorganic compounds containing copper such as cuprous oxide and cuprous thiocyanate as marine organism adhesion inhibitors to prevent the adhesion of marine organisms such as seaweed. Paint compositions have been widely used.
[0003]
However, in recent years, the use of organotin compounds has been regulated due to the problem of environmental pollution. As an alternative to this, a coating composition comprising a rosin, various hydrolyzable resins, a slightly water-soluble resin, and the like and a biofouling inhibitor has been used and proposed, but its biofouling inhibitory ability is still insufficient. Not enough.
[0004]
The performance required for a paint composition that exhibits the marine organism adhesion inhibitory effect over a long period of time is that the biologically active substance used as an inhibitor has a high adhesion inhibitory effect on many types of marine organisms, Degradable resin causes hydrolysis in seawater to gradually dissolve the coating film from the surface.
[0005]
Furthermore, it is necessary to deplete the coating film so that the affinity of the physiologically active substance for seawater and the affinity of the hydrolyzable resin for seawater can effectively exert the physiologically active substance. Therefore, when a compound as a bioadhesion inhibitor has a molecular structure that has a high adhesion-inhibiting effect on marine fouling organisms and is combined with a hydrolyzable resin, the entire coating film is coated. This composite material can be developed for the first time if it has an affinity that does not cause a defect in the membrane and depletes the marine organism adhesion inhibitor.
[0006]
Here, many proposals have been made mainly on either the marine organism adhesion inhibitor containing no metal and the hydrolyzable resin. For example, as a marine organism adhesion inhibitor, (C ₆ H ₅ ) ₄ An underwater antifouling paint using a tetraphenylboron compound represented by BX (where X represents a potassium atom, an ammonium group, or a quaternized organic nitrogen group) is known (see Patent Document 1). ).
[0007]
The underwater antifouling paint containing a tetraphenylboron compound described in Patent Document 1 has poor stability and cannot sufficiently exhibit antifouling properties. Therefore, a paint composition for inhibiting adhesion of marine organisms. It could not be a thing. In particular, according to the description of Patent Document 1, when a mild steel sheet coated with the underwater antifouling paint is immersed in the sea, marine organisms have begun to adhere to the mild steel sheet around nine months after the immersion. The antifouling property over the period could not be exhibited.
[Patent Document 1]
Japanese Patent Publication No. 54-1571 (Claim 1, Table 1, Table 2)
[0008]
On the other hand, a hydrolyzable resin is most preferable as a resin that releases a marine organism adhesion inhibitor into seawater for a long period of time and maintains the effect of preventing organism adhesion for a long period of time. Many coating compositions of such a hydrolysis type have been proposed (see Patent Documents 2 and 3).
The erodible bottom paint described in Patent Document 2 is “at least 5 × 10 ^-4 A water-insoluble, seawater-erodable, organotin-free, film-forming film having a hydrolysis rate of milliequivalents and thereby at least an erosion rate of the antifouling paint in seawater of at least 2 microns per month. It is composed of a specific polymer binder and a poison (composed of coalescing) (see claim 1 of Patent Document 2).
However, Patent Literature 2 describes "tributyltin fluoride, triphenyltin hydroxy, triphenyltin fluoride" or the like as the poison (see column 10, line 3 to line 8 of Patent Literature 2). ). The poisons described in Patent Literature 2 are substances that adversely affect the environment as sex-disrupting substances.
The resin for an antifouling paint described in Patent Document 3 is described as follows. ² R ³ R ⁴ A specific vinyl monomer (A) in a form blocked by the above and a copolymerizable vinyl monomer (B) other than this vinyl monomer are obtained by copolymerizing at a specific ratio, and a specific number average It has a molecular weight (see claim 1 of Patent Document 3). According to Patent Document 3, an antifouling paint is formed by mixing the antifouling paint resin, an antifouling agent such as an organotin compound, and a metal compound such as zinc suboxide and zinc chromate (Patent Document 3). Page 7, upper left column, line 7 to upper right column, line 3). Such metal compounds such as organotin compounds and zinc chromate have an adverse effect on the environment, and have various adverse effects on the human body in the long term.
[0009]
[Patent Document 2]
Japanese Patent Publication No. 5-32433 (Claim 1)
[Patent Document 3]
JP-A-63-215780 (Claim 1)
Further, a specific carboxylic acid is represented by -SiR ¹ R ² R ³ (A) and Y- (CH ₂ CH ₂ O) n-R ⁴ (Patent Document 4). A coating composition containing a copolymer of a monomer mixture containing a monomer (B) represented by Formula (1) and triphenylboronpyridine has been proposed.
[0010]
In Patent Document 4, triphenylboronpyridine (also referred to as pyridyl-triphenylborane) is mainly used as a biofouling inhibitor, and none of these can maintain its antifouling performance for a long period of time. . Pyridyl-triphenylborane is an effective physiologically active substance, but has a high affinity for seawater, so it elutes into seawater at a high rate, and tends to be consumed from the coating film in a short period of time. The effect cannot be maintained.
[Patent Document 4]
Japanese Patent Application Laid-Open No. 8-277372 (Claim 1)
[0011]
Also, diaryl-type organoboron compounds are known as antifouling agents (see Patent Documents 5 and 6). Specifically, the “organic boron compound as an antifouling agent” described in Patent Document 5 is a compound having a specific structure including diphenylalkylboronpyridine (refer to Claim 1 of Patent Document 5). The harmful-water biological control agent described in Patent Document 6 contains a diaryl (pyridinio or isoquinolinio) boron complex as an active ingredient. "
[0012]
The antifouling agents described in Patent Literatures 5 and 6 have an effect as a biofouling inhibitor, but have not reached the level of maintaining their antifouling performance for a long period of time (see Table 11 of Patent Literature 5, See Table 4 of Patent Document 6).
[Patent Document 5]
Patent No. 3034053 (Claim 1)
[Patent Document 6]
JP-A-9-323909 (Claim 1)
[0013]
[Problems to be solved by the invention]
The present invention is extremely environmentally safe, which does not cause coating defects such as peeling or cracks over time after immersion in seawater, is consumed at a constant rate, and exhibits a good marine organism adhesion inhibiting effect over a long period of time. It is an object of the present invention to provide an excellent coating composition, an antifouling coating film, an underwater structure, and a method for forming an antifouling coating film on an underwater structure.
[0014]
[Means for Solving the Problems]
When developing a coating composition for inhibiting marine organism adhesion, a coating film composed of a hydrolyzable resin and a marine organism adhesion inhibitor must be treated as a single composite material.
[0015]
It can be said that the coating film composed of the hydrolysis resin and the physiologically active substance is an interactive type slightly water-soluble composite material. It has a mechanism in which the resin after hydrolysis is slightly dissolved in seawater, and the biologically active substance, which is an anti-adhesion agent for marine organisms, also becomes active for the first time when it is slightly dissolved in seawater. It is of the nature that exerts.
[0016]
Therefore, both exhibit their effects by contact with water molecules, and therefore have an affinity for water molecules of each substance, but a coating made of those substances exhibits its function as a slightly water-soluble composite material. Is what you do.
[0017]
The present inventors have paid attention to a coating composition comprising a combination of a specific useful organic silyl resin and a specific marine organism adhesion inhibitor as a hydrolyzable resin.
[0018]
As a result of intensive studies by the present inventors, while using a specific resin having an organic silyl group introduced into the molecule thereof as the hydrolyzable resin, a marine organism adhesion inhibitor represented by the above-mentioned general formula (2) is used. A coating composition using one or more of the compounds used as essential components is extremely excellent in environmental safety, has high coating hardness when forming a coating, and has coating defects such as peeling and cracks after immersion in seawater. And release the compound represented by the general formula (2) into seawater at a rate effective for inhibiting the adhesion of marine organisms. The present inventors have found that a hydrolyzable self-polishing coating composition capable of exhibiting a living organism adhesion inhibiting effect over a long period of time can be obtained, and have completed the present invention.
[0019]
That is, the present invention relates to a polymer PA obtained by polymerizing one or more of the monomers A represented by the following general formula (1), and / or one or more of the monomers A. A resin M composed of a copolymer PAB obtained by copolymerizing the monomer A and one or two or more monomers B other than the copolymerizable monomer A, and a resin represented by the following general formula (2): A coating composition comprising one or more of the following borane compounds.
Embedded image

(In the general formula (1), R ¹ ~ R ³ Are each a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different from each other. X is an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group, a fumaroyloxy group, or an itaconoyloxy group. )
Embedded image

(In the general formula (2), Y is a halogen, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, n is an integer of 0 to 3, and n is 2 or 3. At this time, Y may be the same or different. ⁴ Represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, a hydroxy group, or halogen.
In the general formula (2), R ⁵ Represents a group represented by the following general formula (3), 5,6,7,8-tetrahydroisoquinoline group, isoquinoline group, general formula (4) or general formula (5) which can be substituted with halogen. )
Embedded image

(In the general formula (3), Z is a halogen, an alkyl group having 1 to 8 carbon atoms, a phenyl group, or an acetyl group. M is an integer of 0 to 3.)
Embedded image

(In the general formula (4), R ⁶ Represents a linear or branched alkyl group having 3 to 24 carbon atoms. )
Embedded image

(In the general formula (5), R ⁷ Represents a linear or branched alkyl group having 3 to 24 carbon atoms. R ⁸ Represents a linear or branched alkyl group having 3 to 24 carbon atoms. )
In a preferred embodiment of the present invention, the coating composition contains a rosin compound in a ratio of 0.1 to 90% by mass relative to the resin M,
In a preferred embodiment of the present invention, the coating composition comprises a marine organism adhesion inhibitor that inhibits adhesion of marine organisms,
In a preferred aspect of the present invention, the marine organism adhesion inhibitor in the coating composition is a metal-free organic inhibitor.
Another aspect of the present invention is an antifouling coating film formed from the coating composition according to the present invention.
In still another aspect of the present invention, the surface of an underwater structure that comes into contact with seawater or freshwater is coated with an antifouling coating film formed from the coating composition according to any one of claims 1 to 4. An underwater structure characterized by the following.
Another aspect of the present invention is a method for preventing an underwater structure, comprising applying the coating composition according to any one of claims 1 to 4 to a surface of the underwater structure to form an antifouling coating film. This is a method for forming a dirty coating film.
[0020]
In the coating composition of the present invention, as one of its essential components, a polymer PA composed of one or more of the monomers A represented by the general formula (1), and / or the monomer A copolymer PAB of one or more of A and one or more of monomer B copolymerizable with the monomer A is used.
[0021]
As represented by the general formula (1), the monomer A has an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group [mainly a monoalkyl (carbon number) 1-6) ester maleinoyloxy group], fumaroyloxy group [mainly monoalkyl (C1-6) ester fumaroyloxy group], or itaconoyloxy group [mainly monoalkyl (C1-6) ester] Itaconoyloxy group] and a triorganosilyl group.
[0022]
In the triorganosilyl group, three hydrocarbon groups (R ¹ ~ R ³ ) May be the same or different groups. Specifically, methyl, ethyl, propyl, butyl or the like having 20 or less carbon atoms, linear or branched, unsubstituted alkyl group and substituted alkyl group; substituents such as cyclopropyl, cyclohexyl, etc. A cyclic alkyl group which may have a substituent; an aryl group which may have a substituent such as a phenyl group; and a polycyclic aryl group which may have a substituent such as a naphthyl group. .
[0023]
Examples of the substituent of the substituted alkyl group include halogen, an aryl group, an acyl group, an alkoxy group, an allyloxy group, a nitro group, and an amino group. Examples of the substituent of the substituted aryl group include a halogen, an alkyl group, and an acyl group. , An alkoxy group, an allyloxy group, a nitro group and an amino group.
[0024]
Examples of such a monomer A include those having a (meth) acryloyloxy group in the molecule, such as trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tri-n-propylsilyl (meth) acrylate, and tri-i-yl. Propylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, tri-i-butylsilyl (meth) acrylate, tris-butylsilyl (meth) acrylate, tri-n-amylsilyl (meth) acrylate, trii-amylsilyl (meth) Acrylate, tri-n-hexylsilyl (meth) acrylate, tri-n-octylsilyl (meth) acrylate, tri-n-dodecylsilyl (meth) acrylate, tri-n-icosasilyl (meth) acrylate, triphenylsilyl (meth) acryle , Tri p- methylphenyl silyl (meth) acrylate, tribenzylsilyl (meth) acrylate, tri-2-methoxyethyl silyl (meth) acrylate.
[0025]
Other examples having a (meth) acryloyloxy group in the molecule include ethyl dimethylsilyl (meth) acrylate, dimethyl n-propylsilyl (meth) acrylate, dimethyl i-propylsilyl (meth) acrylate, and n-butyldimethyl. Silyl (meth) acrylate, s-butyldimethylsilyl (meth) acrylate, i-butyldimethylsilyl (meth) acrylate, t-butyldimethylsilyl (meth) acrylate, n-amyldimethylsilyl (meth) acrylate, i-amyldimethyl Silyl (meth) acrylate, n-icosyldimethylsilyl (meth) acrylate, n-octyldi-n-butylsilyl (meth) acrylate, dii-propylstearylsilyl (meth) acrylate, dicyclohexylphenylsilyl (meth) Acrylate, lauryl diphenylsilyl (meth) acrylate, ethyl di-n-octylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, cyclohexyldi-p-tolylsilyl (meth) acrylate, di-tert-butylmethylsilyl (meth) acrylate Acrylate, n-icosa-di-o-nitrophenylsilyl (meth) acrylate, i-amyl dim-chlorophenylsilyl (meth) acrylate, ethylmethyl n-propylsilyl (meth) acrylate, i-amyl t-butylmethylsilyl (meth) A) acrylate, o-cyanophenylcyclohexylnaphthylsilyl (meth) acrylate, and the like.
[0026]
As those having a maleinoyloxy group in the molecule, trimethylsilylmethyl malate, triethylsilyl n-propylmalate, trii-propylsilylmethylmalate, trii-propylsilyl n-amylmalate, tri-n-propylsilyl n- Amyl maleate, tri-i-propylsilyl i-amyl malate, tri-n-butylsilyl n-butyl malate, t-butyl difersilyl methyl malate, t-butyl diphenylsilyl n-butyl malate, tri-n-butyl silyl 2-ethylhexyl malate, tris -Butylsilyl n-octylmalate, tri-n-amylsilylphenylmalate, tri-i-amylsilylbenzylmalate, tri-n-dodecylsilyl o-nitrophenylmalate, tri-n-icosylsilyl p-tolylmalate, Riphenylsilyl 2-methoxyethylmalate, tribenzylsilyl m-bromophenylmalate, tri2-methoxyethylsilylcyclohexylmalate, ethyldimethylsilylmethylmalate, dimethyl n-propylsilylmethylmalate, dimethyli-propyl Silyl n-amylmalate, n-butyldimethylsilyl i-amylmalate, s-butyldimethylsilylphenylmalate, i-butyldimethylsilylcyclohexylmalate, t-butyldimethylsilyl o-N, N-dimethylaminophenylmalate, n-amyldimethylsilyl t-butylmalate, i-amyldimethylsilyl 2-methoxyethylmalate, n-icosadimethylsilyl2-ethoxyethylmalate, ethyldi-n-octylsilyl p-tolylmalate, -Butyldiphenylsilyl 3-methoxycyclohexylmalate, di-t-butylmethylsilyl i-propylmalate, n-icosa-dio-nitrophenylsilyl m-fluorophenylmalate, i-amyldim-chlorophenylsilyl 2-ethylhexyl Maleate, ethylmethyl n-propylsilyl i-butylmalate, i-amyl t-butylmethylsilyl s-butylmalate, o-cyanophenylcyclohexylnaphthylsilylmethyl malate and the like. Among these, an organosilane substituted with a monoalkyl ester maleinoyloxy group having an alkyl group having 1 to 6 carbon atoms is preferable.
[0027]
As those having a fumaroyloxy group in the molecule, methyltrimethylsilyl fumarate, tri-i-propylsilylmethyl fumarate, tri-i-propylsilyl n-amyl fumarate, ditriethylsilyl fumarate, tri-n-propyl silyl n-amyl fumarate, tri i -Propylsilyl i-amyl fumarate, tri-n-butylsilyl 2-ethylhexyl fumarate, tri-n-butylsilyl n-butyl fumarate, t-butyldiphenylsilylmethyl fumarate, tris-butylsilyl n-octyl fumarate, tri-i-butylsilyl n-butyl fumarate, t-butyldiphenylsilyl n-butyl fumarate, tri-n-amylsilylphenyl fumarate, tri-i-amylsilylbenzyl fumarate, tri-n-dodecylsilyl o-nitrofu Nil fumarate, tri-n-icosasilyl p-tolyl fumarate, triphenylsilyl 2-methoxyethyl fumarate, tribenzylsilyl m-bromophenyl fumarate, tri-2-methoxyethylsilylcyclohexyl fumarate, ethyldimethylsilylmethyl fumarate, ethyl Dimethyl n-propylsilyl fumarate, dimethyl i-propylsilyl n-amyl fumarate, n-butyldimethylsilyl i-amyl fumarate, s-butyldimethylsilylphenyl fumarate, i-butyldimethylsilylcyclohexyl fumarate, t-butyldimethylsilyl o -N, N-dimethylaminophenyl fumarate, n-amyldimethylsilyl t-butyl fumarate, i-amyldimethylsilyl 2-methoxyethyl fumarate, n-icosadimethyi Silyl 2-ethoxyethyl fumarate, ethyl di-n-octylsilyl p-tolyl fumarate, t-butyldiphenylsilyl 3-methoxycyclohexyl fumarate, benzylcyclohexyl di-p-tolylsilyl fumarate, di-t-butylmethyl i-propyl fumarate N-icosa-di-o-nitrophenylsilyl m-fluorophenyl fumarate, i-amyl dim-chlorophenylsilyl 2-ethylhexyl fumarate, ethyl methyl n-propylsilyl i-butyl fumarate, i-amyl t-butyl methyl Silyl s-butyl fumarate, o-cyanophenylcyclohexylnaphthylsilylmethyl fumarate and the like can be mentioned. Among these, an organosilane substituted with a monoalkylester fumanoyloxy group having an alkyl group having 1 to 6 carbon atoms is preferable.
[0028]
As those having an itaconoyloxy group in the molecule, trimethylsilylmethyl itaconate, triethylsilyl n-propyl itaconate, tri-n-propylsilyl n-amylitaconate, tri-i-propylsilyl i-amylitaconate, tri-n- Butylsilyl 2-ethylhexylitaconate, tris-butylsilyl n-octylitaconate, trin-amylsilylphenylitaconate, trii-amylsilylbenzylitaconate, trin-dodecylsilyl o-nitrophenylitaconate, tri-n- Icosasilyl p-tolyluitaconate, triphenylsilyl 2-methoxyethyl itaconate, tribenzylsilyl m-bromophenylitaconate, tri-2-methoxyethylsilylcyclohexylitaconate, ethyl dimethyl Silylmethyl itaconate, dimethyl n-propylsilylmethyl itaconate, dimethyl i-propylsilyl n-amilytaconate, n-butyldimethylsilyl i-amilyitaconate, s-butyldimethylsilylphenylitaconate, i-butyldimethylsilyl Cyclohexylitaconate, t-butyldimethylsilyl o-N, N-dimethylaminophenylitaconate, n-amyldimethylsilyl t-butylitaconate, i-amyldimethylsilyl 2-methoxyethylitaconate, n-icosyldimethylsilyl 2-ethoxyethyl itaconate, ethyl di-n-octylsilyl p-tolylitaconate, t-butyldiphenylsilyl 3-methoxycyclohexylitaconate, di-t-butylmethyl i-propyl itaconate, n Icosa-di-o-nitrophenylsilyl m-fluorophenylitaconate, i-amyldim-chlorophenylsilyl 2-ethylhexylitaconate, ethylmethyl n-propylsilyl i-butylitaconate, i-amyl t-butylmethylsilyl s- Butyl itaconate, o-cyanophenylcyclohexylnaphthylsilylmethyl itaconate, and the like. Among these, an organosilane substituted with a monoalkyl ester itaconoyloxy group having an alkyl group having 1 to 6 carbon atoms is preferable.
[0029]
Other monomers B copolymerizable with these monomers A include, for example, vinyl esters such as acrylic esters, methacrylic esters, styrene, vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate. And various vinyl monomers such as vinyltoluene, α-methylstyrene, crotonic esters, and itaconic esters.
[0030]
The resin M in the present invention has various aspects, for example, a homopolymer obtained by polymerizing one type of the monomer A, a copolymer obtained by copolymerizing two or more types of the monomer A, A copolymer obtained by polymerizing a monomer mixture of one or more of monomer B other than monomer A and one or more of monomer A copolymerizable with monomer A. Polymers and resins composed of mixtures of these polymers can be mentioned.
There is no particular limitation on the monomer ratio between the monomer A and the other monomer A in the copolymer obtained by copolymerizing two or more types of the monomer A.
In the monomer mixture, the proportion of the monomer A and the other monomer B copolymerizable with the monomer A can be appropriately set according to the purpose of use of the coating composition. Is preferably 1 to 95% by mass and the other monomer B copolymerizable therewith is 5 to 99% by mass.
[0031]
The polymer PA or copolymer PAB can be obtained by polymerizing in the presence of a vinyl polymerization initiator by a known polymerization method, for example, various methods such as solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization. it can. When the resin M composed of the polymer PA and / or the copolymer is used for coating, it is convenient to dilute the resin M with an organic solvent to obtain a resin solution having an appropriate viscosity. It is desirable to employ a polymerization method.
[0032]
As the above-mentioned vinyl polymerization initiator, an initiator used in ordinary polymerization can be selected and used according to the polymerization method. Specific examples include 2,2'-azobis-isobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1 '-Azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis- (2-amidinopropane) Azobis initiators such as dihydrochloride, and peroxide initiators such as benzoyl peroxide, t-butylperoxy (2-ethylhexanoate), t-butylperoxyisopropyl carbonate, and t-butylperoxybenzoate And the like.
[0033]
The organic solvent may be selected from various organic solvents according to the type of the monomer and the polymerization temperature, and may be used alone or in combination of two or more. Specifically, aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; ester solvents such as ethyl acetate, butyl acetate, and isobutyl acetate; methyl ethyl ketone; Examples include ketone solvents such as isobutyl ketone and cyclohexanone, and alcohol solvents such as ethanol, isopropanol and butanol.
[0034]
The molecular weight of each of the polymer PA and the copolymer PAB obtained by such a method is desirably in the range of 1,000 to 300,000 by weight average. If the molecular weight is too low, it is difficult to form a normal coating film, and if it is too high, a large number of thinners are required at the time of coating, so that a number of coating times are required to obtain the required concentration. . Further, the viscosity of the resin solution is advantageously 150 poise or less at 25 ° C., and for that purpose, the solid content of the resin solution is in the range of 5 to 90% by mass, preferably 15 to 85% by mass. It is better to be.
[0035]
The coating composition of the present invention contains, as an essential component, a polymer PA and / or a copolymer PAB obtained by the above method as a resin component. Other polymers may be used in small amounts.
[0036]
In the coating composition according to the present invention, a rosin compound may be used together with the resin M. Here, examples of the rosin compound include rosin, rosin derivatives, and rosin metal salts. For example, as rosin, tall rosin, gum rosin, wood rosin, and the like, as rosin derivatives, hydrogenated rosin, maleated rosin obtained by reacting rosin with maleic anhydride, formylated rosin, polymerized rosin, and the like, as rosin metal salts Examples include zinc rosinate, calcium rosinate, copper rosinate, magnesium rosinate, and other reaction products of a metal compound with rosin.
[0037]
In the present invention, one or two or more of these rosin compounds are selected and used. The amount of the rosin compound is 0.1 to It is good to be 90 mass%, preferably 0.1 to 80 mass%.
[0038]
When the amount of the rosin compound is excessive, the ability to form a coating film is reduced, and defects such as cracks and peeling are liable to occur in the coating film, and it is difficult to obtain effective marine organism adhesion preventing performance. When the amount is too small, the effectiveness of the rosin compound is not exhibited.
[0039]
The resin M in the present invention does not contain a metal in the resin M as long as the resin M is composed of the polymer PA and / or the copolymer PAB. As long as it satisfies and does not inhibit the object of the present invention, it is allowed to contain other polymers and / or copolymers containing no metal, and furthermore, as long as the object of the present invention, particularly, environmental safety is not impaired. In the above, it is permissible to contain one or more selected from other known hydrolysable resins containing metals. As the hydrolyzable resin,
The following general formula (6):
Embedded image

(However, in the general formula (6), R ⁹ Is a hydrogen atom or a methyl group, M ¹ Is Mg, Zn or Cu, R ¹⁰ Represents an organic acid residue having an unsaturated group selected from oleic acid, elaidic acid, linoleic acid, linolenic acid, stearic acid, ricinoleic acid, ricinoeladic acid, brassic acid, and erucic acid. A) a hydrolysis resin obtained by polymerizing a monomer mixture containing a metal-containing polymerizable monomer represented by, or a side chain terminal of the hydrolysis resin or another known hydrolysis resin,
General formula (7) below;
Embedded image

(However, in the general formula (7), m is 0, 1 or 2, and n is [(metal valence number) -1]. ² Represents Si, Cu or Zn, L represents an alkyl group, O (O =) C-R ¹¹ Or a group represented by -R ¹² -CO-CH ₂ -CO-R ^Thirteen Represents a group represented by R ¹¹ Represents a hydrocarbon group having 10 or more carbon atoms; ¹² Represents a divalent group consisting of an alkylene group or a phenyl derivative; ^Thirteen Represents a monovalent group consisting of an alkyl group or a phenyl derivative. ) Containing a hydrolysable resin,
Or, the following general formula (8);
Embedded image

(However, in the general formula (8), Rp represents a base resin, M ³ Represents a divalent metal atom. )
And a metal-containing hydrolyzable resin represented by
[0040]
In the present invention, the amount of the known hydrolyzable resin used is 0.1 to 90% by mass in terms of a solid content ratio with respect to the silyl group-containing copolymer represented by the general formula (1). Preferably, the content is 0.1 to 80% by mass.
[0041]
If the amount of the hydrolyzable resin used in combination is too large, the resins will not be compatible with each other, and the coating film forming ability will be reduced, and the coating film will be susceptible to defects such as cracks and peeling. It is difficult to obtain. When the amount is too small, the effectiveness of the hydrolyzable resin is not exhibited.
[0042]
Further, the coating composition of the present invention uses, as an essential component, a borane compound selected from one or more represented by the general formula (2). Examples of the borane compound selected from one or more represented by the general formula (2) include 4-isopropylpyridyl-diphenylmethylborane, 4-phenylpyridyl-diphenylborane, and diphenylborane-n-octadecylamine. it can. The amount of such a borane compound used is usually in the range of 0.01 to 60% by mass, preferably 0.1 to 40% by mass in the solid content of the coating composition.
[0043]
If the amount of the borane compound is too small, the effect of inhibiting the adhesion of marine organisms cannot be expected. If the amount is too large, defects such as cracks and peeling are liable to occur in the coating film, so that a favorable inhibitory effect cannot be obtained.
[0044]
In the present invention, if necessary, in addition to the borane compound selected from one or more represented by the general formula (2), another marine organism adhesion inhibitor known in the paint industry can be used in combination.
[0045]
Other marine organism adhesion inhibitors are composed of metal-free organic inhibitors. Examples of such organic inhibitors include N-trihalomethylthiophthalimide, dithiocarbamic acid, and N-arylmaleimide. , 3-substituted amino-1,3-thiazolidine-2,4-dione, dithiocyano compounds, triazine compounds, copper thiocyanate, pyrithione compounds and others.
[0046]
Specifically, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyl-N'-dichlorophenyl Urea, 4,5-dichloro-N-octyl-isothiazolin-3-one, N- (fluorodichloromethylthio) phthalimide, N, N-dimethyl-N'-phenyl-N'-fluorodichloromethylthiosulfamide, tetramethyl Thiuram disulphide, 2,4,6-trichlorophenylmaleimide, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, diiodomethylparatolyl sulfone, 2- (4-thiazolyl) benzo Examples thereof include imidazole, zinc salt of 2-pyridinethiol-1-oxide and copper salt.
[0047]
Furthermore, by combining the metal-free resin M and the metal-free organic inhibitor, the metal-free hydrolyzable resin and the metal-free marine organism adhesion inhibitor are formed on the environment and safety. Paint composition.
[0048]
Here, “does not include a metal” means that a metal element having a problem with environmental safety, such as copper, tin, and mercury, is not included as one of the constituent elements of an organic inhibitor (organic compound). It does not mean that it does not contain even trace amounts of the above-mentioned metals as impurities derived from the synthesis raw materials of organic inhibitors.
[0049]
Oil components such as silicone oil and liquid paraffin can be added to the coating composition of the present invention as needed for the purpose of adjusting the dissolution rate. Specifically, examples of the oil component include dimethyl silicone oil, methylphenyl silicone oil, polyether-modified silicone oil, petrolatum, and polybutene.
[0050]
In the coating composition of the present invention, as long as the object of the present invention is not impaired, a red iron oxide, a coloring agent such as a pigment and a dye such as titanium oxide, zinc oxide, and talc, which are commonly used in a coating, and a paint commonly used The anti-sagging agent, anti-segregation agent, anti-settling agent, antifoaming agent, etc., as well as plasticizers, other resins, solvents, etc., can be added as necessary. Examples of the plasticizer include chlorinated paraffin, dialkyl phthalate, tricresyl phosphate, and triphenyl phosphate.
[0051]
The coating composition of the present invention can be manufactured by using a conventionally known coating manufacturing method, and the coating method is also applied by means such as spray coating, brush coating, roller coating, and dipping. Can be.
The surface on which the coating composition of the present invention is applied is at least a draft surface of an underwater structure. Examples of the underwater structure include a ship, a buoy, a fixed fish net, a cultured fish net, various water pipes, a pollution control membrane, an offshore oilfield drilling well, a pier, a pipeline, an undersea cable, a heat exchanger, a dam, and a water absorption screen. it can.
[0052]
The coating composition of the present invention comprises, as essential components, a specific hydrolyzable resin having a triorganosilyl group in a side chain and a borane compound selected from one or more represented by the above general formula (2). The antifouling coating, which is a composite material composed of it, has been designed over a long period of time because its affinity with seawater or fresh water is very well designed for the wear resistance of the antifouling coating. Demonstrate excellent adhesion inhibition performance.
[0053]
In addition, the coating composition of the present invention not only has no coating defects such as peeling and cracks, but also is consumed at a constant and favorable rate, and forms a resin residue layer on the coating film surface because it is a self-polishing coating. Without this, it shows very good recoating properties as compared with conventional non-hydrolysable paints. Furthermore, when other metal-containing marine organism adhesion inhibitors are not used in combination, there is no danger of pitting corrosion on aluminum.
[0054]
Further, since the antifouling coating film according to the present invention has good solubility, the surface of the antifouling coating film can always be kept smooth. For this reason, the fuel efficiency of ships and the like can be reduced, and it is also possible to contribute to the prevention of global warming due to carbon dioxide. Furthermore, in the coating composition of the present invention, a good marine organism adhesion inhibiting effect can be exhibited without using cuprous oxide in combination. Although it cannot be colored vividly due to the use of such a paint composition, it can be colored in any vivid color and is a coating composition having excellent design properties.
[0055]
【Example】
Next, the present invention will be specifically described with reference to Production Examples, Examples, and Comparative Examples. In addition, the part in an example is a mass part, and molecular weight is polystyrene conversion weight average molecular weight by GPC.
[0056]
The monomer A (A1 to A8) used in the production example is a monomer represented by the above general formula (1), and R in the general formula (1) ¹ ~ R ³ And X are as shown in Table 1 below.
[0057]
[Table 1]

[0058]
[Production Examples 1 to 5]
In a flask equipped with a stirrer, a solvent a was charged according to the composition shown in Table 2 below, and the temperature was raised to a predetermined reaction temperature. The mixture was dropped into the flask over 3 hours, and after the dropping was completed, the mixture was kept at the same temperature for 30 minutes. Then, a mixture of the solvent b and the polymerization catalyst b was added dropwise over 20 minutes, and stirring was continued at the same temperature for 2 hours to complete the polymerization reaction. Finally, a diluting solvent is added to dilute each resin solution S ₁ ~ S ₅ Got. In Table 2, "Perbutyl I" (trade name, manufactured by NOF Corporation) as a polymerization catalyst is t-butyl peroxyisopropyl carbonate, and "Vova 9" is (Showa Shell Chemical Co., Ltd.) Trade name) vinyl ester monomer.
[0059]
[Production Example 6]
In a flask equipped with a stirrer, a solvent a, a monomer A, another monomer B, and a polymerization catalyst a were charged according to the composition shown in Table 2 below, and the temperature was raised to a predetermined reaction temperature while stirring. Stirring was continued at the same temperature for 6 hours to complete the reaction. Next, the resin solution S is diluted with a diluting solvent. ₆ Got.
[0060]
[Production Example 7]
A monomer A, another monomer B, and a polymerization catalyst a were charged into a heat-resistant and pressure-resistant container in accordance with the composition shown in Table 2 below. The mixture was warmed and shaken at the same temperature for 8 hours to complete the reaction. Next, a diluting solvent was added and shaken for 8 hours to dissolve the resin solution S. ₇ Got.
[0061]
[Table 2]

[0062]
[Examples 1 to 24]
Resin solution S ₁ ~ S ₇ , Each component was mixed according to the composition shown in the following Tables 3 to 5 (the numerical values in the table are% by mass), mixed and dispersed with a homomixer of 2,000 rpm, and the coating composition of 20 kinds was obtained. I got something. In each table, “TSF-4445” (trade name of Toshiba Silicone Co., Ltd.) is a polyether-modified silicone oil, and “Dispalon A630-20XN” (trade name of Kusumoto Kasei Co., Ltd.) and “ Benton SD-2 (trade name of National Red Co., Ltd.) is an additive for preventing dripping. “Resin A”, “Resin B” and “Resin C” in Table 5 were prepared as follows. In addition, the biological adhesion inhibitor in each table relates to the compound represented by the general formula (2).
[0063]
[Production procedure of “Resin A”]
A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 20 parts of propylene glycol methyl ether and 40 parts of xylene, and the temperature was raised to 100 ° C. while stirring. Next, a mixture obtained by mixing 10 parts of propylene glycol methyl ether and 10 parts of xylene with 30 parts of zinc oleate methacrylate, 5 parts of methyl methacrylate, 60 parts of ethyl acrylate, and 1.5 parts of t-butyl perocrate from the dropping funnel was added. The solution was dropped at a constant speed over time. After completion of the dropwise addition, 1 part of t-butyl peroctate and 10 parts of xylene were added dropwise over 1 hour, and the mixture was further stirred for 2 hours, and then xylene 10 was added to obtain “Resin A”.
[0064]
[Production procedure of “Resin B”]
30 parts of xylene and 15 parts of n-butanol were charged into a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer, and the temperature was raised to 110 ° C while stirring. Next, a mixture of 7.2 parts of acrylic acid, 4.5 parts of methyl methacrylate, 38.3 parts of ethyl acrylate and 1 part of azobisisobutyronitrile was dropped at regular intervals over 4 hours. After the completion of the dropwise addition, a mixture of 0.3 part of t-butylperoxy-2-ethylhexanoate and 5 parts of xylene was added dropwise over 1 hour, and the mixture was further stirred for 3 hours to obtain a resin solution. To 100 parts of the resin solution, 10 parts of copper acetate and 5.6 parts of oleic acid were added, and the mixture was reacted for 6 hours while removing water generated under reflux, 6.3 parts of xylene was added, and the mixture was cooled. I got it.
[0065]
[Production procedure of “Resin C”]
23 parts of xylene, 30 parts of butyl acetate, and 30 parts of n-butanol were charged into a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer, and the temperature was raised to 105 ° C. while stirring. Next, a mixture of 15 parts of methacrylic acid, 40 parts of methoxyethyl acrylate, 5 parts of methyl methacrylate and 8 parts of azobisisobutyronitrile was dropped at a constant speed over 4 hours. After the completion of the dropwise addition, a mixture of 6 parts of xylene and 1 part of azobisisobutyronitrile was added dropwise for 1 hour, and the mixture was further stirred for 1 hour to obtain a resin solution. To 100 parts of this resin solution, 7.5 parts of zinc oxide, 5.3 parts of water, 7.5 parts of butyl acetate and 7.5 parts of n-butanol were added, and the mixture was stirred at 100 ° C. for 20 hours to obtain “Resin C”. Obtained.
[0066]
[Table 3]

[0067]
[Table 4]

[0068]
[Table 5]

[0069]
[Comparative Examples 1 to 5]
Using the polymer solutions S1 to S5, the respective components were mixed according to the composition shown in the following Table 6 (the numerical values in the table are% by mass), and mixed and dispersed with a homomixer of 2,000 rpm to obtain three kinds of paints. A composition was prepared. In Table 5, “TSF-4445”, “Dispalon A630-20XN” and “Benton SD-2” are the same as those in Tables 2 and 3 described above.
[0070]
[Table 6]

[0071]
The coating compositions of Examples 1 to 34 and Comparative Examples 1 to 7 were subjected to a coating film wear test, a marine organism adhesion inhibition test, an adhesion test, and a crack resistance test in the following manner.
[0072]
[Coating wear test]
After the preparation, each coating composition stored in an oven at 50 ° C. for 2 weeks was applied to the front surface of a steel plate (100 mm × 100 mm × 1 mm) with a rust-proof coating on the back surface so that the dry film thickness was 300 μm. A test piece was prepared by spray painting and drying in a room at a temperature of 20 ° C. for one week. After fixing the above test piece on the outer surface of a cylindrical drum having a diameter of 50 cm, it was immersed 1 m below the sea surface in Yura Bay, Sumoto City, Hyogo Prefecture, and rotated by a motor so that the peripheral speed of the drum became 16 knots. The exhausted coating thickness was measured every 3 months for 12 months. In addition, the average thickness (μm / month) of coating film thickness consumption was calculated. In addition, if the average coating film thickness consumption speed is 3 μm / month or more, it correlates with good antifouling performance.
[0073]
[Marine organism adhesion inhibition test]
A tar epoxy-based anticorrosive paint is applied twice on both sides of a blasted steel plate (100 mm x 300 mm x 1 mm) by spray coating so as to have a dry film thickness of 125 µm each time, and a vinyl-based sealer coat having a dry film thickness of 50 µm. It painted so that it might become. On both sides, each coating composition was applied by spray coating so that the dry film thickness was 150 μm on one side, and dried for one week in a constant temperature / humidity room at a temperature of 20 ° C. and a humidity of 65% to prepare test pieces. did. The test piece was immersed in seawater for 12 months in Osaka Bay, Takaishi City, Osaka Prefecture, and the ratio of the occupied area (adhered area) of the attached organisms on the test coating film was measured over time.
[0074]
[Adhesion test]
A tar epoxy-based anticorrosive paint is applied twice on both sides of a blasted steel plate (100 mm x 300 mm x 1 mm) by spray coating so as to have a dry film thickness of 125 µm each time, and a vinyl-based sealer coat having a dry film thickness of 50 µm. It painted so that it might become. On this, each coating composition was applied by spray coating so that the dry film thickness became 150 μm, and dried for one week in a constant temperature / humidity room at a temperature of 20 ° C. and a humidity of 65% to prepare a test piece. . The test piece was immersed in artificial seawater, pulled up after 3 months, 6 months, 9 months, and 12 months, and subjected to a 2 mm-spaced goban test. The adhesion was evaluated as ○ (pass) when the number of peeled pieces by this test was 25/25, and × (failed) when the number of peeled pieces was 24 or less / 25 pieces.
[0075]
[Crack resistance test]
In the adhesion test, when the test piece was pulled up from artificial seawater, the coating film was visually observed to check for the occurrence of cracks. A sample without cracks was evaluated as ○ (pass), and a sample with cracks was evaluated as x (fail).
[0076]
[Table 7]

[0077]
[Table 8]

[0078]
[Table 9]

[0079]
[Table 10]

[0080]
[Table 11]

[0081]
As is clear from the results of Tables 6 to 11, in each of the coating compositions of Comparative Examples 1 to 7, as seen in Comparative Examples 1 to 7, the coating film consumption rate, the marine organism adhesion inhibition performance, Although the film physical properties were unsatisfactory, each of the coating compositions of Examples 1 to 34 of the present invention showed satisfactory results in any of the tests. From these results, the coating compositions of the present invention also showed satisfactory results. The product was found to be excellent in environmental safety and provided with good performance, comprising an organic silyl hydrolyzable resin and a marine organism adhesion inhibitor.
[0082]
【The invention's effect】
According to the present invention, even after immersion in seawater or freshwater, a coating film defect such as peeling or cracking does not occur over time, is consumed at a constant speed, and has a favorable marine organism adhesion inhibiting effect over a long period of time. The present invention can provide a coating composition, an antifouling coating film, an underwater structure, and a method for forming an antifouling coating film on an underwater structure, which are extremely excellent in environmental safety.

Claims (7)

A polymer PA obtained by polymerizing one or more of the monomers A represented by the following general formula (1), and / or one or more of the monomers A and the monomers A A resin M made of a copolymer PAB obtained by copolymerizing one or two or more monomers B other than the copolymerizable monomer A, and one kind of a borane compound represented by the following general formula (2) Or a coating composition comprising two or more kinds.

(In the general formula (1), each of R ^{1 to} R ³ is a hydrocarbon group having 1 to 20 carbon atoms and may be the same or different from each other. X is acryloyloxy A methacryloyloxy group, a maleinoyloxy group, a fumaroyloxy group or an itaconoyloxy group.)

(In the general formula (2), Y is a halogen, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, n is an integer of 0 to 3, and n is 2 or 3. Wherein Y may be the same or different, and R ⁴ is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and 2 to 2 carbon atoms. And 8 represents an alkynyl group, a hydroxy group, or a halogen.
In the general formula (2), R ⁵ is the following general formula (3), a 5,6,7,8-tetrahydroisoquinoline group which can be substituted with halogen, an isoquinoline group, a general formula (4) or a general formula (5) Shows any group. )

(In the general formula (3), Z is a halogen, an alkyl group having 1 to 8 carbon atoms, a phenyl group, or an acetyl group. M is an integer of 0 to 3.)

(In the general formula (4), R ⁶ represents a linear or branched alkyl group having 3 to 24 carbon atoms.)

(In the general formula (5), R ⁷ represents a linear or branched alkyl group having 3 to 24 carbon atoms. R ⁸ represents a linear or branched alkyl group having 3 to 24 carbon atoms.) The coating composition according to claim 1, comprising a rosin compound in a ratio of 0.1 to 90% by mass based on the resin M. The coating composition according to claim 1 or 2, further comprising a marine organism adhesion inhibitor that inhibits adhesion of marine organisms. The coating composition according to claim 3, wherein the marine organism adhesion inhibitor is a metal-free organic inhibitor. An antifouling coating film formed from the coating composition according to claim 1. An underwater structure, wherein the surface of the underwater structure that comes into contact with seawater or freshwater is covered with an antifouling coating film formed from the coating composition according to any one of claims 1 to 4. object. A method for forming an antifouling coating for an underwater structure, comprising applying the coating composition according to any one of claims 1 to 4 to a surface of the underwater structure to form an antifouling coating.