JP4790208B2 - Epoxy resin composition, anticorrosion film formed from the composition, base material with anticorrosion film coated with the anticorrosion film, and anticorrosion method for the base material - Google Patents

Description

【００６１】
液状炭化水素樹脂
本発明に用いられる主剤成分（Ａ）は、さらに液状炭化水素樹脂を含有していることも好ましい。
【００６２】
そのような液状炭化水素樹脂（液状石油樹脂）は、常温（１５〜２５℃の温度）で液状であり、粘度が５００〜４００，０００mPa・s／２５℃の範囲である液状炭化水素樹脂であり、そのような液状炭化水素樹脂としては、具体的には、脂肪族炭化水素（Ｃ９系石油樹脂）、芳香族炭化水素（Ｃ５系石油樹脂）、クロマン樹脂、キシレン樹脂、トルエン樹脂やこれらの変性物などが挙げられる。
【００６３】
本発明においては、このような液状炭化水素樹脂は、１種または２種以上組み合わせて用いることができる。このように２種以上の液状炭化水素樹脂を組み合わせて用いる場合には、液状炭化水素樹脂の前記分子量は、その平均値で示す。
【００６４】
前記液状炭化水素樹脂のうちでは、エポキシ樹脂との相溶性が良好なものであることが必要であり、好ましくは、芳香族炭化水素（Ｃ５系石油樹脂）、キシレン樹脂、トルエン樹脂を用いることが望ましい。
【００６５】
このような液状炭化水素樹脂の平均分子量等は、得られる塗料の塗装硬化条件（例：常乾塗装あるいは焼付け塗装等）などにもより、一概に決定されないが、その数平均分子量が通常１５０〜７２０であり、粘度が３０〜７００，０００mPa・s／２５℃のものが用いられる。
【００６６】
代表的な前記液状炭化水素樹脂は、具体的に、
脂肪族炭化水素（Ｃ９系石油樹脂）としては、ネシレスＥＰＸ−Ｌ、ネブケムＮＬ−１０、ネブケムＮＬ−２０、ネブケムＮＬ−３０、ネシレスＥＰＸ−Ｔ６（商品名、いずれもNevcin Polymers co.製）などを挙げることができる。
【００６７】
芳香族炭化水素（Ｃ５系石油樹脂）としては、マルカクリアーＨ、マルカクリアーＶ（商品名、いずれも丸善石油（株）製）などを挙げることができる。
【００６８】
キシレン樹脂としては、ニカノールＤＳ，ＬＬＬ，ＬＬ，Ｌ，Ｈ（商品名、いずれも三菱ガス化学（株）製）、ハイゾールＳＡＳＬＨ（商品名、新日本石油化学（株）製）などを挙げることができる。
【００６９】
クロマン樹脂としては、エスクロンＬ−５，Ｌ−２０（商品名、いずれも新日鉄化学（株）製）などを挙げることができる。
【００７０】
トルエン樹脂としては、エポジールＬ（商品名、アンカーケミカル（株）製）などを挙げることができる。
【００７１】
本発明においては、これら前記液状炭化水素樹脂を１種または２種以上組み合わせて用いてもよい。
【００７２】
着色顔料、体質顔料
本発明のさらに好ましい態様において主剤成分（Ａ）に含有される着色顔料および／または体質顔料のうち、前記着色顔料は、特に制限はなく、従来公知の着色顔料、たとえばカーボンブラック、二酸化チタン、弁柄、酸化鉄、水酸化鉄、群青等の無機顔料、シアニンブルー、シアニングリーン等の有機顔料が挙げられる。着色顔料は、１種単独で、あるいは２種以上組み合わせて用いることができる。
【００７３】
また、前記体質顔料は、従来公知の体質顔料であり、たとえば沈降性硫酸バリウム、炭酸カルシウム、カリ長石、カオリン、アルミナホワイト、クレー、タルク、ベントナイト、炭酸マグネシウム、炭酸バリウム、シリカ微粉末、雲母粉、ガラスフレーク，ステンレスフレーク，アルミフレーク，プラスティックフレーク等が挙げられる。本発明に用いられる体質顔料としては、沈降性硫酸バリウム、炭酸カルシウム、カリ長石、雲母粉、ガラスフレークが用いられるが好ましい。体質顔料は、１種単独で、あるいは２種以上組み合わせて用いることができる。
【００７４】
本発明のエポキシ樹脂組成物を、使用済み核燃料貯蔵用プールに用いる場合、着色顔料としては二酸化チタン、体質顔料としてはシリカ微粉末を用いることが好ましい。このような顔料に限定されるのは、低融点金属やハロゲンの水への溶出量が制限されるためである。
【００７５】
着色顔料および／または体質顔料は、主剤成分（Ａ）１００重量部に対して、通常５〜８０重量部、好ましくは２０〜７０重量部、さらに好ましくは４０〜６０重量部の量で用いられる。
【００７６】
その他の成分
本発明に用いられる主剤成分（Ａ）には、前記液状エポキシ樹脂（ａ１）、液状炭化水素樹脂、さらに着色顔料および／または体質顔料以外に、その他の成分として、繊維物質、タレ止め・沈降防止剤、特開平２−２９８５６３号記載の界面活性剤、防錆顔料などを適宜添加することができる。
【００７７】
（繊維物質）
前記繊維物質としては、アスベスト、ウォラスナイト、セピオライト、チタン酸カリウムウィスカ、ケイ酸カルシウムウィスカ、塩基性硫酸マグネシウム、植物繊維、ガラスファイバー、カーボンファイバー、合成繊維などが挙げられ、好ましくは、ウォラスナイト、セピオライト、チタン酸カリウムウィスカが用いられる。
【００７８】
このような繊維物質としては、ＮＹＡＤ １２５０（ウォラスナイト；NYCO Minerals Inc製）、ミルコンＭＳ−２−２（セピオライト；昭和鉱業（株）製）、ティスモ−Ｄ（チタン酸カリウムウィスカ；大塚化学（株）製）が挙げられる。
【００７９】
繊維物質は、この主剤成分（Ａ）中（１００重量％）に、例えば、０．１〜１０重量％の量で含有されていてもよい。
【００８０】
（タレ止め・沈降防止剤）
前記タレ止め・沈降防止剤としては、有機粘度系Ａｌ、Ｃａ、Ｚｎのステアレート塩、レシチン塩、アルキルスルホン酸塩などの塩類、ポリエチレンワックス、アマイドワックス、水添ヒマシ油ワックス系、ポリアマイドワックス系および両者の混合物、合成微粉シリカ、酸化ポリエチレン系ワックス等が挙げられ、好ましくは、ポリアマイドワックス、合成微粉シリカ、酸化ポリエチレン系ワックス、有機粘度系が用いられる。
【００８１】
このようなタレ止め・沈降防止剤としては、楠本化成（株）製の「ディスパロン305」、「ディスパロン4200-20」等の他、「ディスパロン6650」、伊藤精油（株）製の「ＡＳＡＴ−２５０Ｆ」等の商品名で上市されているものが挙げられる。
【００８２】
タレ止め・沈降防止剤は、この主剤成分（Ａ）中（１００重量％）に、例えば、０．１〜１０重量％の量で含有されていてもよい。
【００８３】
（界面活性剤）
前記界面活性剤としては、特開平２−２９８５６３号記載の界面活性剤が用いることができ、具体的には、下記一般式（１），（２），（３），（４），（５）
【００８４】
【化１】

【００８５】
（式中Ｍは水素、金属、塩基性窒素含有化合物を示す。）
で表される酸基（またはその塩）を少なくとも１個有する界面活性剤が用いられる。
【００８６】
前記界面活性剤は、この主剤成分（Ａ）中（１００重量％）に、例えば、１〜５重量％の量で含有されていてもよい。
【００８７】
（防錆顔料）
前記防錆顔料としては、クロム酸系，モリブデン酸系，リン酸系，ホウ酸系，フェライト系，鉛酸系の顔料などが挙げられる。本発明においては、リン酸系顔料を用いること好ましく、そのようなものとしては、リン酸系のリン酸亜鉛、トリポリリン酸アルミニウムが挙げられる。
【００８８】
このような防錆顔料としては、ＬＦボウセイ２Ｐ−ＤＬ（キクチカラー（株）製）、Ｋ−ホワイト＃８２（テイカ（株）製）が挙げられる。
【００８９】
防錆顔料は、着色顔料および／または体質顔料１００重量％に対し、例えば、５〜３０重量％の量で含有されていてもよい。
【００９０】
また、本発明のエポキシ樹脂組成物は、大気中および水中（海水中を含む）でも塗装可能であるため、該エポキシ樹脂組成物に含有される主剤成分（Ａ）には、樹脂成分を溶解するためなどに用いられる溶剤を実質的に含有しない。仮に、本発明のエポキシ樹脂組成物を大気中での塗装にのみ使用するのであれば、実用上の弊害（皮膜から溶剤の抜けが悪くなり、皮膜形成上不具合が生ずる等）が認められない程度の溶剤を主剤成分（Ａ）に添加することも可能であり、さらに、薄膜で被覆するか，薄膜で数回塗って厚膜を形成するならば溶剤を多く含むことも可能である。
【００９１】
このような主剤成分（Ａ）は、前記各成分を前記の量で配合し、三本ロールまたはハイスピードディスパーで攪拌・混練り等して得られる。
【００９２】
＜硬化剤成分（Ｂ）＞
本発明のエポキシ樹脂組成物は、前記主剤成分（Ａ）および硬化剤成分（Ｂ）を含有してなり、この硬化剤成分（Ｂ）は、アミン系硬化剤（ｂ１）を含有する。さらに液状炭化水素樹脂を含有していることも好ましい。
【００９３】
アミン系硬化剤（ｂ１）は、フェノール類と、ホルマリンと、アミン化合物とのマンニッヒ縮合反応で形成されたマンニッヒ変性アミン類（ｂ１−１）、および／または脂肪族ポリアミン類（ｂ１−２）であることが好ましい。
【００９４】
本発明のさらに好ましい態様においては、この硬化剤成分（Ｂ）は、着色顔料および／または体質顔料を含有している。
【００９５】
マンニッヒ変性アミン類（ b1-1 ）
前記マンニッヒ変性アミン類（b1-1）は、フェノール類と、ホルムアルデヒドと、アミン化合物とのマンニッヒ（脱水）縮合反応で形成されるが、
このフェノール類としては、不飽和置換基含有フェノール、飽和置換基含有フェノールが挙げられる。
【００９６】
不飽和置換基含有フェノールとしては、分子中に少なくとも１個のモノヒドロキシフェニル基を含み、かつフェニル基水素の一部、すなわち該水素１〜５個が不飽和炭化水素基で置換されたものなどが挙げられる。
【００９７】
該不飽和炭化水素基としては、例えば、炭素数１〜１０程度のアルキレン基、前記アルキレン基を含有したフェニル基などが挙げられる。
【００９８】
このような不飽和置換基含有フェノールとしては、具体的には、例えば、カルダノール（cardanol）、イソプロペニルフェノール、ジイソプロペニルフェノール、ブテニルフェノール、イソブテニルフェノール、シクロヘキセニルフェノール、
モノスチレン化フェノール（Ｃ₆Ｈ₅-ＣＨ＝ＣＨ-Ｃ₆Ｈ₄-ＯＨ）、
ジスチレン化フェノール（(Ｃ₆Ｈ₅-ＣＨ＝ＣＨ)₂-Ｃ₆Ｈ₃-ＯＨ）、
などが挙げられる。
【００９９】
このようなマンニッヒ変性アミン類（ｂ１−１）は、硬化剤成分（Ｂ）１００重量％中に、通常、１０〜４０重量％、好ましくは２０〜３０重量％の量で含まれていることが好ましい。
【０１００】
さらに具体的には、前記アルキルフェノールとしては、メチルフェノール（ｏ，ｍ，ｐ−クレゾール）、エチルフェノール、ブチルフェノール、ターシャリブチルフェノール、オクチルフェノール、ノニルフェノール、ドデシルフェノール、ジノニルフェノール等の１価フェノールが挙げられ、
ハロゲン化フェノールとしては、クロルフェノール等の１価フェノールが挙げられる。
【０１０１】
これらのうちでは、１価の単核フェノールが好ましい。
【０１０２】
アミン化合物としては、脂肪族系、脂環族系、芳香族系、複素環系などの何れでもよい。
【０１０３】
脂肪族系アミン化合物としては、例えば、アルキレンポリアミン、ポリアルキレンポリアミン、その他の脂肪族系ポリアミン類などが挙げられ、
より具体的には、前記アルキレンポリアミンとしては、例えば、式：Ｈ₂Ｎ−Ｒ¹−ＮＨ₂（Ｒ¹：炭素数１〜１０の炭化水素基側鎖を１個または複数個有していてもよい主鎖炭素数１〜１２の二価炭化水素基）で表され、例えば、メチレンジアミン、エチレンジアミン、１，２−ジアミノプロパン、１，３−ジアミノプロパン、１，４−ジアミノブタン、１，５−ジアミノペンタン、１，６−ジアミノヘキサン、１，７−ジアミノヘプタン、１，８−ジアミノオクタン、１，９−ジアミノノナン、１，１０−ジアミノデカン等が用いられる。
【０１０４】
前記ポリアルキレンポリアミンとしては、例えば、式：Ｈ₂Ｎ−(Ｃ_mＨ_2mＮＨ)_nＨ（ｍ：１〜１０の整数、ｎ：２〜１０、好ましくは２〜６の整数）で表され、より具体的には、例えば、ジエチレントリアミン、ジプロピレントリアミン、トリエチレンテトラミン、トリプロピレンテトラミン、テトラエチレンペンタミン、テトラプロピレンペンタミン、ペンタエチレンヘキサミン、ノナエチレンデカミン、トリメチルヘキサメチレンジアミン等が挙げられる。
【０１０５】
その他の脂肪族系ポリアミン類としては、特公昭４９−４８４８０号公報第２４欄などに記載されているような、テトラ（アミノメチル）メタン、テトラキス（２−アミノエチルアミノメチル）メタン、１，３−ビス（２’−アミノエチルアミノ）プロパン、トリエチレン−ビス（トリメチレン）ヘキサミン、ビス（３−アミノエチル）アミン、ビスヘキサメチレントリアミン[Ｈ₂Ｎ(ＣＨ₂)_nＮＨ(ＣＨ₂)_nＮＨ₂、ｎ＝６]、等が挙げられる。
【０１０６】
脂環族系のアミン類としては、より具体的には、１，４−シクロヘキサンジアミン、４，４’−メチレンビスシクロヘキシルアミン、４，４’−イソプロピリデンビスシクロヘキシルアミン、ノルボルナジアミン、ビス（アミノメチル）シクロヘキサン、ジアミノジシクロヘキシルメタン、イソホロンジアミン、メンセンジアミン（ＭＤＡ）等が挙げられる。
【０１０７】
芳香族系のアミン類としては、ビス（アミノアルキル）ベンゼン、ビス（アミノアルキル）ナフタレン、ベンゼン環に結合した２個以上の１級アミノ基を有する芳香族ポリアミン化合物、その他の芳香族系ポリアミン類などが挙げられる。
【０１０８】
この芳香族系アミン類として、より具体的には、例えば、ビス（シアノエチル）ジエチレントリアミン、ｏ−キシリレンジアミン、ｍ−キシリレンジアミン（ＭＸＤＡ）、ｐ−キシリレンジアミン、フェニレンジアミン、ナフチレンジアミン、ジアミノジフェニルメタン、ジアミノジエチルフェニルメタン、
２，２−ビス（４−アミノフェニル）プロパン、４，４’−ジアミノジフェニルエーテル、４，４’−ジアミノベンゾフェノン、４，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルスルホン、２，２’−ジメチル−４，４’−ジアミノジフェニルメタン、２，４’−ジアミノビフェニル、２，３’−ジメチル−４，４’−ジアミノビフェニル、３，３’−ジメトキシ−４、４’−ジアミノビフェニル、ビス（アミノメチル）ナフタレン、ビス（アミノエチル）ナフタレン等が挙げられる。
【０１０９】
複素環系のアミン類としては、より具体的には、Ｎ−メチルピペラジン［ＣＨ₃-Ｎ（ＣＨ₂ＣＨ₂）₂ＮＨ］、モルホリン［ＨＮ（ＣＨ₂ＣＨ₂）₂Ｏ］、１，４−ビス−（８-アミノプロピル）-ピペラジン、ピペラジン−１，４−ジアザシクロヘプタン、１−（２’−アミノエチルピペラジン）、１−［２’−（２”−アミノエチルアミノ）エチル］ピペラジン、１，１１−ジアザシクロエイコサン、１，１５−ジアザシクロオクタコサン等が挙げられる。
【０１１０】
その他、本発明で使用可能なアミン化合物としては、例えば、特公昭４９−４８４８０号公報第１２頁２４欄第４３行〜第１４頁第２８欄第２５行に記載の芳香族系のアミン類（アミン化合物）を使用することもできる。
【０１１１】
その他、ジエチルアミノプロピルアミン、ポリエーテルジアミン等が挙げられる。
【０１１２】
本発明では、これらのアミン化合物は、１種または２種以上組み合わせて用いることができる。
【０１１３】
これらアミン化合物のうちでは、脂肪族系に属する前記アルキレンポリアミン、ポリアルキレンポリアミンが好ましく、さらには、エチレンジアミン、ジエチレンポリアミンが好ましい。
【０１１４】
前記マンニッヒ脱水縮合反応の際には、例えば、フェノール類の１種であるカルダノールと、ホルムアルデヒドと、アミン化合物のキシリレンジアミンとを、理論的には等モルで用いればよいが、通常、フェノール類１モルに対して、ホルムアルデヒドは０．５〜２．５モルの量で、アミン化合物は０．５〜２．５モルの量で用いて、５０〜１８０℃程度の温度で３〜１２時間程度加熱保持すればよい。
【０１１５】
このように不飽和置換基含有フェノールと、ホルムアルデヒドと、アミン化合物とをマンニッヒ縮合反応させて得られるマンニッヒ変性アミン類（b1-1）のうちでは、前記不飽和置換基含有フェノールのカルダノールと、ホルムアルデヒドと、アミン化合物の前記アルキレンポリアミンまたはポリアルキレンポリアミンとを反応させて得られるマンニッヒ変性アミンが好ましい。
【０１１６】
これらマンニッヒ変性アミン類（b1-1）は、通常Ｎ．Ｖ．４０〜１００％に調製され、アミン価（mgKOH/g）が３００〜５００の範囲にあると、基材との付着性、耐水性、防食性に優れた皮膜を形成することができるため好ましい。
【０１１７】
このようなマンニッヒ変性アミン類（b1-1）としては、具体的には、
エアー・プロダクツ社製：アンカミン２４３２（ＮＶ４３．５％、アミン価３８７）、アンカミン２０８９Ｍ（ＮＶ１００％、アミン価３６８）、
コグニスジャパン社製：バーサミンＦ２０（ＮＶ１００％、アミン価４００〜４８０）、バーサミンＩ−３６８（ＮＶ１００％、アミン価３７０〜４００）、バーサミンＭ−１（ＮＶ１００％、アミン価３７５〜４２５）、
シェル社製：エピキュアー３５４９（ＮＶ１００％）、エピキュアー３３７８（ＮＶ７４．５％）、
Ｗｉｔｃｏ社製：ＴＬ０７１２（ＮＶ９４．３％、アミン価７０５）、
旭電化(株)製：アデカハードナーＥＨ３４２Ｍ（ＮＶ４０．２％、アミン価３０７）、アデカハードナーＥＨ３４２Ｍ１７（ＮＶ３３．３％、アミン価３８６）、アデカハードナーＥＨ３５０（ＮＶ５２．８％、アミン価３８５）、アデカハードナーＥＨ３５１（ＮＶ４６．９％、アミン価３０６）、
三和化学工業(株)：サンマイドＷ−３０００（ＮＶ１００％、アミン価３４０）、サンマイドＷ−１０００（ＮＶ１００％、アミン価３４０）、サンマイドＷ−５００（ＮＶ１００％、アミン価２８０）、サンマイドＣＸ−１０２（ＮＶ８９．８％、アミン価２８８）、
大都産業(株)：ダイトクラールＳＫ９００ＦＣＢ（ＮＶ１００％、アミン価３８５）、
大日本インキ化学工業（株）：ラッカマイドＶ６−２２１（ＮＶ１００％、アミン価４２０）
などが挙げられる。本発明では、これらのマンニッヒ変性アミン類（b1-1）は、１種または２種以上組み合わせて用いることができる。
【０１１８】
また、本発明においては、マンニッヒ変性アミン類（b1-1）が、水に難溶性または不溶性であるマンニッヒ変性アミンであることが望ましい。マンニッヒ変性アミン類（b1-1）が、水に容易に溶解するものであると、得られるエポキシ樹脂組成物を湿潤面に塗布することが困難になる。
【０１１９】
このようなマンニッヒ変性アミン類（b1-1）は、硬化剤成分（Ｂ）１００重量％中に、通常、１０〜４０容量％、好ましくは２０〜３０容量％の量で含まれていることが好ましい。
【０１２０】
マンニッヒ変性アミン類（b1-1）が硬化剤成分（Ｂ）に前記の量で含有されることにより、本発明に係るエポキシ樹脂組成物は、その硬化速度、低温硬化性が改善される。
【０１２１】
脂肪族ポリアミン類（ b1-2 ）
前記マンニッヒ変性アミン類（b1-1）と共に硬化剤成分（Ｂ）に含有される前記脂肪族ポリアミン類（b1-2）としては、例えば、アルキレンポリアミン、ポリアルキレンポリアミン、その他の脂肪族系ポリアミン類などが挙げられる。
【０１２２】
具体的には、前記アルキレンポリアミンとしては、例えば、式：Ｈ₂Ｎ−Ｒ¹−ＮＨ₂（Ｒ¹：炭素数１〜１０の炭化水素基側鎖を１個または複数個有していてもよい主鎖炭素数１〜１２の二価炭化水素基）で表され、例えば、メチレンジアミン、エチレンジアミン、１，２−ジアミノプロパン、１，３−ジアミノプロパン、１，４−ジアミノブタン、１，５−ジアミノペンタン、１，６−ジアミノヘキサン、１，７−ジアミノヘプタン、１，８−ジアミノオクタン、１，９−ジアミノノナン、１，１０−ジアミノデカン等が用いられる。
【０１２３】
前記ポリアルキレンポリアミンとしては、例えば、式：Ｈ₂Ｎ−(Ｃ_mＨ_2mＮＨ)_nＨ（ｍ：１〜１０の整数、ｎ：２〜１０、好ましくは２〜６の整数）で表され、より具体的には、例えば、ジエチレントリアミン、ジプロピレントリアミン、トリエチレンテトラミン、トリプロピレンテトラミン、テトラエチレンペンタミン、テトラプロピレンペンタミン、ペンタエチレンヘキサミン、ノナエチレンデカミン、トリメチルヘキサメチレンジアミン等が挙げられる。
【０１２４】
その他の脂肪族系ポリアミン類としては、特公昭４９−４８４８０号公報第２４欄などに記載されているような、テトラ（アミノメチル）メタン、テトラキス（２−アミノエチルアミノメチル）メタン、１，３−ビス（２’−アミノエチルアミノ）プロパン、トリエチレン−ビス（トリメチレン）ヘキサミン、ビス（３−アミノエチル）アミン、ビスヘキサメチレントリアミン[Ｈ₂Ｎ(ＣＨ₂)_nＮＨ(ＣＨ₂)_nＮＨ₂、ｎ＝６]、等が挙げられる。
【０１２５】
本発明においては、これらの脂肪族ポリアミン類（b1-2）は、１種または２種以上組み合わせて用いることができる。
【０１２６】
これら脂肪族ポリアミン類（b1-2）は、通常Ｎ．Ｖ．４０〜１００％に調製され、アミン価（mgKOH/g）が３００〜５００の範囲にあると、基材との付着性、耐水性、防食性に優れた皮膜を形成することができるため好ましい。このような脂肪族ポリアミン類（b1-2）のアミノ基の活性水素当量(g/equiv)は、一概に決定されないが、通常８０〜２５０のものが用いられる。
【０１２７】
脂肪族ポリアミン類（b1-2）としては、具体的には、例えば、「ＡＣＩハードナー（Ｒ）Ｋ−３９」（ＰＴＩジャパン社＝ＩＢＰＴＲジャパン社製）、「サーウェットＲ」、「アンカミン１７８４」（いずれもエアープロダクツジャパン（株）製）、「アデカハードナーＥＨ２４０」,「アデカハードナーＥＨ２７０」（いずれも旭電化（株）製）などが挙げられる。本発明では、これらの脂肪族ポリアミン類は、１種または２種以上組み合わせて用いることもできる。
【０１２８】
また、本発明において、脂肪族ポリアミン類（b1-2）は、水に難溶性または不溶性である脂肪族ポリアミン類であることが望ましい。脂肪族ポリアミン類（b1-2）が、水に容易に溶解するものであると、得られるエポキシ樹脂組成物を湿潤面に塗布することが困難になる。
【０１２９】
この脂肪族ポリアミン類（b1-2）は、硬化剤成分（Ｂ）１００重量％中に、通常、１０〜４０重量％、好ましくは２０〜３０重量％の量で含まれていることが好ましい。
【０１３０】
常温硬化性を有する脂肪族ポリアミン類（b1-2）を前記の量で含有し、または前記マンニッヒ変性アミン類（b1-1）を前記の量で含有することにより、本発明のエポキシ樹脂組成物は硬化速度の調整が可能であり、大気中または水中における使用条件に対応した該塗料組成物を調製することができる。さらに、前記（b1-1）、（b1-2）と、前記樹脂成分（液状エポキシ樹脂（ａ１）および液状炭化水素樹脂）とを前記の量で含有することにより、基材への付着性、耐水性に優れ、かつ基材の腐食を効果的に防止することができ、特に金属基材（特にステンレス基材）の孔食、隙間腐食、異種金属接触腐食、応力腐食を効果的に防止することができる防食皮膜を形成することができる。
【０１３１】
液状炭化水素樹脂
本発明の硬化剤成分（Ｂ）には、前記したように液状炭化水素樹脂（液状石油樹脂）を含有していることも好ましい。
【０１３２】
この液状炭化水素樹脂としては、前記主剤成分（Ａ）に含有される液状炭化水素樹脂と同様のものを用いることができる。
【０１３３】
本発明においては、前記液状炭化水素樹脂は、エポキシ樹脂組成物に含有される(a1)と(a2)と(b1)と液状炭化水素樹脂との合計量１００重量％中に、通常５〜７０重量％、好ましくは１０〜５０重量％の量で含まれていることが望ましい。
【０１３４】
さらに、前記液状炭化水素樹脂は、本発明のエポキシ樹脂組成物（１００重量％）に１〜５０重量％、好ましくは５〜３０重量％の量で含まれていることが望ましい。
【０１３５】
前記液状炭化水素樹脂が、前記の量で本発明のエポキシ樹脂組成物に含有されることによって、基材との付着性、耐水性、防食性に優れた皮膜を該基材表面に形成することができる。
【０１３６】
着色顔料、体質顔料
本発明のさらに好ましい態様においては、硬化剤成分（Ｂ）には、前記主剤成分（Ａ）に用いられる着色顔料および体質顔料と同様のものを配合してもよい。
【０１３７】
また、着色顔料および／または体質顔料は、硬化剤成分（Ｂ）１００重量部に対して、通常５〜８０重量部、好ましくは２０〜７０重量部、さらに好ましくは４０〜６０重量部の量で用いられる。
【０１３８】
前記主剤成分（Ａ）および／または硬化剤成分（Ｂ）に含有される着色顔料、体質顔料の合計容量は、本発明のエポキシ樹脂組成物１００容量％中には１０〜５０容量％、好ましくは１５〜３０容量％、さらに好ましくは２０〜２５容量％の量で含まれていることが望ましい。
【０１３９】
本発明のエポキシ樹脂組成物に、前記の量で着色顔料、体質顔料が含有されていることにより、該組成物が無溶剤型であっても、塗布作業性に優れる。さらに、塗布後の膜が硬化収縮することによる皮膜応力を緩和し、付着力が低下しない。
【０１４０】
その他の成分
本発明に用いられる硬化剤成分（Ｂ）には、前記マンニッヒ変性アミン類（b1-1）、脂肪族ポリアミン類（b1-2）、さらに着色顔料および／または体質顔料以外に、その他の成分として、繊維物質、タレ止め・沈降防止剤、特開平２−２９８５６３号記載の界面活性剤、特開平２−２５１５７７号記載のポリカルボン酸またはその塩、防錆顔料などを適宜添加することができる
そのような繊維物質、タレ止め・沈降防止剤、特開平２−２９８５６３号記載の界面活性剤、特開平２−２５１５７７号記載のポリカルボン酸またはその塩としては、主剤成分（Ａ）に用いたものと同様のものが使用可能である。
【０１４１】
各成分の添加量は、
繊維物質は、この硬化剤成分（Ｂ）中に、例えば、０．１〜１０重量％の量で含有されていてもよく、
タレ止め・沈降防止剤は、この硬化剤成分（Ｂ）中に、例えば、０．１〜１０重量％の量で含有されていてもよく、
前述したような界面活性剤は、この硬化剤成分（Ｂ）中に、例えば、１〜５重量％の量で含有されていてもよく、
前述したようなポリカルボン酸またはその塩は、この硬化剤成分（Ｂ）中に、例えば、１〜５重量％の量で含有されていてもよく、
防錆顔料は、この硬化剤成分（Ｂ）中に、例えば、５〜３０重量％の量で含有されていてもよく、
本発明に用いられる硬化剤成分（Ｂ）は前記成分を前記の量で配合し、三本ロールまたはハイスピードディスパーで攪拌・混練り等して得られる。
【０１４２】
〔エポキシ樹脂組成物〕
上述のとおり、本発明に係るエポキシ樹脂組成物は、（Ａ）主剤成分および（Ｂ）硬化剤成分を含有してなり、
主剤成分（Ａ）が、液状エポキシ樹脂（ａ１）、およびシランカップリング剤（ａ２）を含有し、さらに、硬化剤成分（Ｂ）が、アミン硬化剤（ｂ１）を含有し、
前記主剤成分（Ａ）および／または前記硬化剤成分（Ｂ）が、液状炭化水素樹脂を含有している。
【０１４３】
前記主剤成分（Ａ）中のエポキシ当量(g/equiv)／前記硬化剤成分（Ｂ）中のアミノ基の活性水素当量(g/equiv)で表される当量比が、０．５〜２．０、好ましくは０．８〜１．５、さらに好ましくは０．９〜１．２となるように配合されることが望ましい。
【０１４４】
本発明のエポキシ樹脂組成物は、このような範囲で主剤成分（Ａ）と硬化剤成分（Ｂ）とが配合されているため、基材との付着性、耐水性、防食性に優れ、特に金属基材（特にステンレス基材）の孔食、隙間腐食、異種金属接触腐食、応力腐食を防止できる防食皮膜を形成することができる。
【０１４５】
さらに、接着剤としても作用して、その皮膜表面にステンレス板を接着させて、局部腐食を長期間安定して防止し、耐食性を付与することができる。
【０１４６】
このような本発明のエポキシ樹脂組成物は、通常、エポキシ樹脂を含有してなる前記主剤成分（Ａ）と、硬化剤成分を含有してなる前記硬化剤成分（Ｂ）との２液型として、それぞれ別の容器に保管される。
【０１４７】
本発明のエポキシ樹脂組成物は、大気中、または水中で塗装する場合においても、使用直前に混合して用いられる。
【０１４８】
なお、エポキシ樹脂用硬化剤として、エポキシ樹脂成分と貯蔵中は反応しないように変性された硬化剤を用いる場合には、ビスフェノール型エポキシ樹脂組成物は、１液型として用いることができる。この変性された硬化剤としては、ケチミンタイプのアミンブロック系硬化剤などが挙げられる。ケチミンタイプのアミンブロック系硬化剤としては、具体的には、エピキュアＨ３０（ジャパンエポキシレジン（株）製）、アデカハードナーＥＨ−２３５Ｒ（旭電化工業（株）製）などを用いることができる。また、このケチミンタイプのアミンブロック系硬化剤は、２液型のエポキシ樹脂組成物において、マンニッヒ変性アミン類（b1-1）、および／または脂肪族ポリアミン類（b1-2）と併用することもできる。
【０１４９】
本発明に係るエポキシ樹脂組成物は、以下に示すように、防食性に優れた皮膜を基材表面に形成できる防食組成物、特にステンレス基材用の防食組成物、またステンレス板をステンレス製構造物の表面に貼り付ける接着剤組成物として有用である。
【０１５０】
［防食皮膜、防食皮膜付き基材、防食方法など］
本発明の防食皮膜(層)は、前記エポキシ樹脂組成物から形成され、硬化後の膜厚は特に限定されるものではないが、２００〜５０００μｍ、好ましくは５００〜２０００μｍであることが望ましい。
【０１５１】
防食皮膜(層)の膜厚が前記範囲であることにより、防食性に優れた皮膜を基材表面に効果的に形成することができる。
【０１５２】
また、本発明に係る防食皮膜付き基材は、前記のように、本発明の防食皮膜で基材表面が被覆されている。そのような基材としては、鉄鋼、非鉄金属（亜鉛、アルミニウム、ステンレス等）などが挙げられ、本発明においてはステンレスに用いることが有用である。従って、本発明の防食皮膜(層)は、前記基材、好ましくはステンレス基材への付着性に優れ、耐水性に優れ、かつ孔食、隙間腐食、異種金属接触腐食、応力腐食を防止することができる。
【０１５３】
このような防食皮膜は、大気中で形成される場合、具体的には、ステンレス基材（例：SUS403）の表面をサンドペーパーで研磨するなどの素地調整を施した後、前記エポキシ樹脂組成物をハケ、ロ−ラー、ヘラ、コテなどにより塗装し、該組成物が硬化することにより形成される。また、防食皮膜が水中で形成される場合、例えば補修塗装やメンテナンス塗装などにおいては、前記エポキシ樹脂組成物をハケ、ヘラ、コテなどにより補修部分等に塗装し、該組成物が硬化することにより形成される。
【０１５４】
本発明の防食方法によれば、前記効果を有する皮膜を形成でき、基材の孔食、隙間腐食、異種金属接触腐食、応力腐食を防止することができる。
【０１５５】
さらに付言すれば、本発明の組成物は、前記したような優れた性能の皮膜を基材表面に形成できるため、海水淡水化装置、海洋構造物のメンテナンスの困難な箇所、ダムや水門のゲート周り、海水・河川水や工業用水を冷却水として使用するプラントなどの配管、貯水槽、貯水タンク、使用済み核燃料貯蔵用プール等に使用可能であり、またさらに、前記腐食を生じた防食皮膜付き基材表面を補修被覆することも可能である。
【０１５６】
また、本発明のエポキシ樹脂組成物は、ステンレスの溶接部や隙間がある箇所に防食塗膜を形成して、ステンレス基材の局部腐食を防止するとともに、さらに接着剤としても作用して、その塗膜表面にステンレス板を接着させて、局部腐食を長期間安定して防止し、耐食性を付与することができる。
【０１５７】
このような補修方法は、特に限定されないが、具体的には、上述のように、溶接部（溶接線）や隙間があるステンレス基材表面に本発明のエポキシ樹脂組成物を塗布し、未硬化の塗膜表面にステンレス板を接着させる。さらに、この上に本発明のエポキシ樹脂組成物を塗布しても良い。
【０１５８】
この補修方法は、ステンレス製構造物であれば特に限定されないが、具体的には、貯水槽、貯水タンク、使用済み核燃料貯蔵用プールなどに対して行われる。これらのうちでも、使用済み核燃料貯蔵用プールは、貯蔵用プール内部の基材表面に溶接部（溶接線）や隙間がある場合には、局部腐食を生じやすい。したがって、本発明のエポキシ樹脂組成物を用いた補修方法によれば、局部腐食を長期間安定して防止し、耐食性を付与することができる。
【０１５９】
本発明の前記組成物は、例えば塗布されて、乾燥・硬化するとき、主剤成分（Ａ）中に含まれるエポキシ樹脂中のエポキシ基が開環して、エポキシ酸素（Ｏ）は水酸基（−ＯＨ）となり、またエポキシ基を形成していた分子末端の炭素は硬化剤中のアミノ基「−ＮＨ₂」などと反応して、「−ＮＨ−」結合などにて硬化剤と結合しているのであろうと推測される。
【０１６０】
【発明の効果】
本発明に係るエポキシ樹脂組成物によれば、基材との付着性、耐水性、防食性に優れ、特に金属基材（特にステンレス基材）の孔食、隙間腐食、異種金属接触腐食、応力腐食を防止できる防食皮膜を形成しうる。
【０１６１】
このエポキシ樹脂組成物は、水中でも塗布可能であり、前記のような優れた特性の皮膜を、海水淡水化装置、海洋構造物のメンテナンスの困難な箇所、ダムや水門のゲート周り、海水・河川水や工業用水を冷却水として使用するプラントなどの配管、水タンク、貯水槽、使用済み核燃料貯蔵用プールなどの基材の防食用途に好適に使用することができる。
【０１６２】
また、本発明のエポキシ樹脂組成物は、ステンレスの溶接部や隙間がある箇所に防食塗膜を形成して、ステンレス基材の局部腐食を防止するとともに、さらに接着剤としても作用して、その塗膜表面にステンレス板を接着させて、局部腐食を長期間安定して防止し、耐食性を付与することができる。
【０１６３】
【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。
【０１６４】
なお、本実施例で用いた使用原料を表２に示す。
【０１６５】
【実施例１〜１１、比較例１〜５】
＜主剤・硬化剤の調製方法、およびエポキシ樹脂組成物の調製方法＞
１．表３および表４に示される、主剤成分に含まれる液状樹脂を容器に配合し、攪拌しながら50℃まで昇温した後、その他の使用原材料をハイスピードディスパーで混練し、実施例および比較例で用いる主剤を調製した。
【０１６６】
なお、比較例１および比較例３は、それぞれ固形樹脂であるエピコート１００１とネオポリマーＥ−１００を、５０℃まで加温したキシレンをディスパーで攪拌しながら少量ずつ添加し、溶液としてから配合した。
【０１６７】
２．表２および表３に示した、硬化剤に含まれる液状樹脂を、攪拌しながら50℃まで昇温し、その他の使用原材料をハイスピードディスパーで混練し、実施例および比較例で用いる硬化剤を調製した。
【０１６８】
３．試験に供試する直前に、前記方法で作成した主剤と硬化剤を、小計量で示される混合比率で、金へらを用いて混合した後、使用した。
＜試験方法：試験板および試験板の調製＞
１．SUS304のステンレス板に、予めスコッチブライト 工業用パットNo.7447で表面を研磨し、表面粗度 Ra 0.3〜0.6μｍに仕上げる。ステンレス板のサイズは、接着強度測定用には70×150×3mm、耐曲げ性試験には50×200×0.3mmのものを用いた。
【０１６９】
２．ステンレス板の長手方向の両端部に、厚さ1mmの3mm×150mmの塩化ビニル板を、両面粘着テープ（日東電工製 両面接着テープＮｏ．５０１５）で固定する。
【０１７０】
３．実施例および比較例のエポキシ樹脂組成物を、大気中、および1昼夜放置した水道水中で、金へらを用い、前記のように貼り付けた１ｍｍ厚さの塩化ビニル板の上をかき取るようにして、ステンレス板表面に膜厚が１ｍｍ程度となるように塗付した。なお、それぞれの塗付条件下で、1週間硬化養生した。
＜評価方法＞
Ａ．ステンレスとの接着強度測定
ＪＩＳ Ｋ ５６００−５−７ ７．３．２に規定されているプルオフ法による付着性測定手順に従い、接着強度を測定した。付着測定用治具は直径２０ｍｍの円筒形のものを用い、塗面を＃８０のサンドペーパーで面を粗くし、エポキシ樹脂系接着剤で付着測定用治具を接着し、毎分２ｍｍで引っ張り、ステンレスとの接着強度を測定した。
Ｂ．耐曲げ性
１．図１の概略図に示される耐曲げ性測定装置１０を用いて、耐曲げ性を測定した。図に示すように、２個の支持台１２，１２の上に、試験板２０を塗面２２が下になるよう載せ、図示しない精密万能試験機（オートグラフＡＧＳ−１０００Ａ、島津製作所製）を用いて、圧子１４を毎分１０ｍｍで下降させる。圧子１４が試験板２０に当たった位置から更に１０ｍｍ圧子１４を下降させる。
【０１７１】
２．圧子１４を１０ｍｍ下降した後、直ちに上げ、塗面２２に割れが生じているかを観察した。
【０１７２】
結果を表５に示す。
【０１７３】
【表２】

【０１７４】
【表３】

【０１７５】
【表４】

【０１７６】
【表５】

【図面の簡単な説明】
【図１】図１は、実施例における耐曲げ性試験に用いられる測定装置の概略図である。
【符号の説明】
１０ 耐曲げ性測定装置
１２ 支持台
１４ 圧子
２０ 試験板
２２ 塗面
Ｒ₁ 圧子１４の先端部半径
Ｒ₂ 支持台１２の湾曲部半径[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an epoxy resin composition, an anticorrosion film formed from the composition, a substrate with an anticorrosion film coated with the anticorrosion film, and a method for preventing corrosion of the substrate. More specifically, the present invention can be applied in the air and in water, and is excellent in adhesion to the substrate and water resistance, and can effectively prevent corrosion of the substrate. In particular, an epoxy resin composition capable of forming an anticorrosion film capable of preventing pitting corrosion, crevice corrosion, dissimilar metal contact corrosion, and stress corrosion of a metal substrate (particularly stainless steel substrate), and an anticorrosion film formed from the composition And a substrate with an anticorrosion coating coated with the anticorrosion coating, and an anticorrosion method for the substrate.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
For many structures installed in the sea, beaches, rivers, lakes, etc., and facilities that use seawater / freshwater, metal base materials have been used in areas where seawater or freshwater is in direct contact. Has been. Such structures and facilities, such as steel sheet pile revetments, steel pipe piles for harbor facilities, piers, dam gates, sluice gates, water tanks, water tanks, etc. are exposed to severe corrosive environments, and anti-corrosion coating, repair coating, or maintenance coating is applied. is needed.
[0003]
These anticorrosion coatings, repair coatings, and maintenance coatings are known to be carried out in the atmosphere by damaging the surroundings, draining, and this coating method is very expensive. For this reason, an underwater anticorrosion paint containing a polyamide-cured epoxy resin, a modified amine-cured epoxy resin, an unsaturated polyester resin, or the like that can reduce the working cost without damming the surroundings and has been put to practical use has been put into practical use.
[0004]
However, when the underwater paint type paint containing each of the above resins is coated on the surface of a steel base material, the water resistance in water, in seawater or on a wet surface of the base material surface is insufficient, or the water resistance is good. Even so, there was a problem that the adhesion of the formed film was insufficient.
[0005]
To solve such a problem,
(1) For a polyester obtained by polycondensation of a dibasic acid and a dihydric alcohol at a certain molar ratio, a polyamine having an amount of amine residues in a certain ratio with respect to the number of acid residues in the polyester. A cured epoxy resin underwater paint curing agent (Patent Document 1; JP 54-1224028 A);
(2) An epoxy resin containing at least one epoxy group in the molecule, and a resin composition having a room temperature curable curing agent as a color developing agent, and an amide compound having a specific structure added to the underwater coating type epoxy Resin composition (Patent Document 2; JP-A-2-29479),
(3) (a) a thermosetting resin curable in water and a color developing material comprising the curing agent thereof, and (b) an underwater paintable underwater curable resin composition containing a polycarboxylic acid having a specific structure or a salt thereof. Product (Patent Document 3; Japanese Patent Laid-Open No. 2-251577),
(4) In a resin composition mainly composed of an underwater curable thermoplastic resin, a resin composition containing a surfactant having a specific structure (Patent Document 4; JP-A-2-298563),
(5) An epoxy resin and an epoxy resin composition containing a phosphorus atom-containing epoxy compound having a specific structure in a resin composition mainly composed of an epoxy resin and its curing agent (Patent Document 5; 1992229),
Has been proposed.
[0006]
In addition, stainless steel is used as cooling water for seawater desalination equipment, places where maintenance of marine structures is difficult, around dams and sluice gates, seawater, river water, and industrial water as a metal substrate that is highly effective in corrosion resistance. Used for piping in plants, water tanks, water tanks, spent nuclear fuel storage pools, etc.
[0007]
However, even in stainless steel structures, local corrosion such as pitting corrosion, crevice corrosion, contact corrosion, and stress corrosion cracking is likely to occur where there are welds or gaps, and the corrosion resistance as originally expected can be obtained. There were cases where it was not possible.
[0008]
In such a case, corrosion resistance can be imparted to the stainless steel substrate by using the compositions (1) to (5), but local corrosion of the stainless steel substrate can be stably prevented for a long time. However, in order to impart corrosion resistance, it is necessary to repair by attaching a stainless steel plate or the like to a welded portion or a portion having a gap. These compositions (1) to (5) had room for improvement in adhesion to the stainless steel plate.
[0009]
Therefore, the above-mentioned problems can be solved, and it can be painted in the air and underwater, and a corrosion-resistant coating film is formed on a stainless steel welded part or a place with a gap to prevent local corrosion of the stainless steel base material. Furthermore, there has been a demand for a composition that can also act as an adhesive and adhere a stainless steel plate to the surface of the coating film.
[0010]
[Patent Document 1]
JP 54-1224028 A
[Patent Document 2]
JP-A-2-29479
[Patent Document 3]
Japanese Patent Laid-Open No. 2-251577
[Patent Document 4]
JP-A-2-298563
[Patent Document 5]
Japanese Patent Laid-Open No. 3-199229
[0011]
OBJECT OF THE INVENTION
The present invention is to solve the problems associated with the prior art as described above,
An object of the present invention is to provide an epoxy resin composition capable of forming a coating film excellent in adhesion to a substrate, water resistance, and corrosion resistance on the surface of the substrate by painting in the air and water.
[0012]
The present invention also provides an epoxy resin composition capable of forming a film capable of preventing pitting corrosion, crevice corrosion, dissimilar metal contact corrosion, and stress corrosion of a metal substrate (particularly a stainless steel substrate) on the surface of the substrate. It is aimed.
[0013]
Furthermore, the present invention forms an anticorrosion coating film at a stainless steel welded part or a portion having a gap to prevent local corrosion of the stainless steel base material, and further acts as an adhesive. It aims at providing the epoxy resin composition which can adhere | attach a board.
[0014]
Another object of the present invention is to provide an anticorrosive composition having the above excellent properties, an anticorrosive film, and a substrate with an anticorrosive film coated with the film.
[0015]
Furthermore, the present invention is a film having excellent characteristics as described above, and uses seawater desalination equipment, places where maintenance of marine structures is difficult, around dams and sluice gates, seawater, river water, and industrial water as cooling water. It is an object of the present invention to provide a method for preventing corrosion of various structures that covers the surface of a substrate such as piping of a plant, a water storage tank, a water storage tank, and a spent nuclear fuel storage pool.
[0016]
In addition, it covers parts that are prone to local corrosion such as pitting corrosion, crevice corrosion, dissimilar metal contact corrosion, stress corrosion cracking, such as welds and gaps of the various structures, and also acts as an adhesive, An object of the present invention is to provide a repair method in which a stainless steel plate is adhered to the surface of the coating film, and a corrosion prevention effect can be stably imparted to various structures for a long period of time.
[0017]
SUMMARY OF THE INVENTION
The epoxy resin composition according to the present invention is
In the epoxy resin composition comprising (A) a main agent component and (B) a curing agent component,
The main component (A) contains a liquid epoxy resin (a1) and a silane coupling agent (a2), and the curing agent component (B) contains an amine-based curing agent (b1),
The main component (A) and / or the curing agent component (B) contains a liquid hydrocarbon resin.
[0018]
It is preferable that the main component (A) and / or the curing agent component (B) contain a color pigment and / or an extender pigment.
[0019]
The amine curing agent (b1) is a Mannich-modified amine (b1-1) formed by a Mannich condensation reaction of phenols, formalin and an amine compound, and / or an aliphatic polyamine (b1-2). It is preferable that
[0020]
The Mannich-modified amines (b1-1) and the aliphatic polyamines (b1-2) are preferably hardly soluble or insoluble in water.
[0021]
The epoxy resin composition according to the present invention is represented by the epoxy equivalent (g / equiv) in the main component (A) / active hydrogen equivalent (g / equiv) of the amino group in the curing agent component (B). The component (A) and the component (B) are preferably contained so that the equivalent ratio is 0.5 to 2.0.
[0022]
Further, the epoxy resin composition according to the present invention has an epoxy equivalent (g / equiv) in the main component (A) / an active hydrogen equivalent (g / equiv) of an amino group in the curing agent component (B). It is also preferred that the (A) and the (B) are contained so that the equivalent ratio represented is 0.8 to 1.5.
[0023]
The epoxy resin composition according to the present invention preferably contains the silane coupling agent (a2) in an amount of 0.1 to 15% by weight in 100% by weight of the composition, It is also preferable that it is contained in an amount of 5% by weight.
[0024]
The color pigment and / or the extender pigment is preferably contained in an amount of 10 to 50% by volume in 100% by volume of the epoxy resin composition, and is contained in an amount of 15 to 30% by volume. Is also preferable.
[0025]
The anticorrosion composition, the anticorrosion composition for a stainless steel substrate, or the adhesive composition for a stainless steel substrate according to the present invention is characterized by comprising the above epoxy resin composition.
[0026]
The anticorrosion film according to the present invention is formed from the above epoxy resin composition.
[0027]
The base material with an anticorrosion film according to the present invention is characterized in that the surface of the base material is coated with the anticorrosion film.
[0028]
The substrate is preferably a metal substrate, particularly a stainless steel substrate.
[0029]
The stainless steel structure with an anticorrosion film according to the present invention is characterized in that the surface of the stainless steel structure is coated with the anticorrosion film.
[0030]
The stainless steel structure is preferably a water tank or a water tank.
[0031]
The repaired stainless steel structure according to the present invention is characterized in that a stainless steel plate is attached to the surface of the stainless steel structure by the epoxy resin composition.
[0032]
The surface of the stainless steel structure preferably has a weld line formed when the stainless steel base material is welded.
[0033]
The stainless steel structure is preferably a water tank or a water tank.
[0034]
The substrate anticorrosion method according to the present invention is characterized in that the surface of the substrate is covered with an anticorrosion film formed from the epoxy resin composition.
[0035]
The base material is preferably a stainless steel base material.
[0036]
The repair method for a stainless steel structure according to the present invention is characterized in that the epoxy resin composition is applied to the surface of the stainless steel structure, and then a stainless steel plate is attached to the surface of the coating film.
[0037]
The surface of the stainless steel structure preferably has a weld line formed when the stainless steel base material is welded.
[0038]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the epoxy resin composition according to the present invention, the anticorrosion film formed from the composition, the substrate with the anticorrosion film coated with the anticorrosion film, and the anticorrosion method for the substrate will be specifically described.
[0039]
The epoxy resin composition according to the present invention comprises (A) a main agent component and (B) a curing agent component,
The main component (A) contains a liquid epoxy resin (a1) and a silane coupling agent (a2), the curing agent component (B) contains an amine curing agent,
Furthermore, the main component (A) and / or the curing agent component (B) contains a liquid hydrocarbon resin.
[0040]
First, each component contained in the epoxy resin composition of the present invention will be described, and the epoxy resin composition of the present invention will be described later.
[0041]
<Main ingredient component (A)>
As described above, the main component (A) used in the present invention contains the liquid epoxy resin (a1) and the silane coupling agent (a2), and preferably further contains a liquid hydrocarbon resin. The liquid hydrocarbon resin can be contained in the curing agent component (B) without being contained in the main component (A).
[0042]
In a further preferred embodiment of the present invention, the main component (A) contains a color pigment and / or an extender pigment.
[0043]
Liquid epoxy resin (a1)
The liquid epoxy resin (a1) is an epoxy resin that is liquid at ordinary temperature (temperature of 15 to 25 ° C.) and has a viscosity in the range of 800 to 25,000 mPa · s, and has two or more epoxy groups in the molecule. And a polymer or oligomer produced by a ring-opening reaction of an epoxy group thereof.
[0044]
Such liquid epoxy resins (a1) include bisphenol type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, cresol type epoxy resins, dimer acid-modified epoxy resins, aliphatic epoxy resins. And epoxy resins such as alicyclic epoxy resins and epoxidized oil-based epoxy resins. Among them, bisphenol type epoxy resins are preferable, bisphenol A type and F type epoxy resins are more preferable, and bisphenol A type epoxy resins are particularly preferably used. When a bisphenol type epoxy resin is used, a film excellent in adhesion to the substrate and corrosion resistance can be formed.
[0045]
Among such liquid epoxy resins (a1), so-called bisphenol A type epoxy resins (epoxy equivalents 150 to 1000 (g / equiv)) are preferable.
[0046]
Examples of particularly preferably used bisphenol A type epoxy resins include bisphenol A diglycidyl ether, bisphenol A polypropylene oxide diglycidyl ether, bisphenol A ethylene oxide diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol A propylene oxide diester. Examples thereof include polycondensation products such as bisphenol A type diglycidyl ether such as glycidyl ether.
[0047]
In this invention, such a liquid epoxy resin (a1) can be used 1 type or in combination of 2 or more types. When two or more kinds of liquid epoxy resins (a1) are used in combination as described above, the molecular weight and epoxy equivalent (g / equiv) of the liquid epoxy resin (a1) are both shown as average values.
[0048]
The average molecular weight or the like of such a liquid epoxy resin (a1) is not generally determined depending on the coating curing conditions (eg, normally dry coating or baking coating) of the resulting coating, but the molecular weight is usually 300 to When the viscosity is 750, the viscosity is 9,000 to 23,000 mPa · s, and the epoxy equivalent is usually in the range of 150 to 300, the coating workability, adhesion to the substrate, water resistance, and corrosion resistance are excellent. It is preferable because a film can be formed.
[0049]
Typical examples of the epoxy resin include “Epicoat 828 (trade name), general name: bisphenol A diglycidyl ether” (manufactured by Shell Co., Ltd., weight average molecular weight of about 360, epoxy equivalent of 180 to 190, viscosity of 12,000 to 15,000 mPa · s / 25 ° C.), “Epototo YDF-170 (trade name), general name: bisphenol F diglycidyl ether” (manufactured by Toto Kasei Co., Ltd., epoxy equivalent 160-180, viscosity 2,000-5) 000 mPa · s / 25 ° C.), “Flep 60 (trade name)” (manufactured by Toraythiol Co., Ltd., epoxy equivalent of about 280, viscosity of about 17,000 mPa · s / 25 ° C.), and the like.
[0050]
In the present invention, even a semi-solid epoxy resin at room temperature can be used as a liquid epoxy resin (a1) by diluting with a liquid hydrocarbon resin described later.
[0051]
As this semi-solid epoxy resin at room temperature, “Epicoat 834 (trade name), general name: bisphenol A type epoxy resin” (manufactured by Japan Epoxy Resins Co., Ltd., epoxy equivalent 230-270, by Gardner / Holtz method) Viscosity P˜U / 25 ° C.).
[0052]
  In the present invention, the liquid epoxy resin (a1) is usually 3 to 30 in the main component (A) (100% by weight).weight%, Preferably 5-10weight% Is desirable.
[0053]
When the epoxy resin (a1) and the liquid hydrocarbon resin are contained in the epoxy resin composition of the present invention in the amounts described above, a film excellent in adhesion to a substrate, water resistance, and corrosion resistance is formed on the base. It can be formed on the material surface.
[0054]
Silane coupling agent (a2)
The silane coupling agent (a2) is
It is desirable that the silane coupling agent contains at least one reactive functional group selected from the group consisting of an amino group, a carboxyl group, a hydroxyl group, an epoxy group and a glycidyl group, and preferably contains an epoxy group. .
[0055]
Examples of such epoxy group-containing silane coupling agents include (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycid. Examples include xylpropylmethyldiethoxysilane.
[0056]
Specific examples of such an epoxy group-containing silane coupling agent include compounds (1) to (5) shown in Table 1 below, preferably (1), (2 It is desirable to use a compound of
[0057]
In the present invention, one or more of these silane coupling agents (a2) may be contained.
[0058]
In the present invention, the silane coupling agent (a2) is desirably contained in the main component (A) in an amount of usually 0.2 to 30% by weight, preferably 1 to 10% by weight.
[0059]
  The silane coupling agent (a2) is 0.1 to 15% by weight, preferably 0.5 to 5% by weight, more preferably 1 to 3% by weight based on 100% by weight of the epoxy resin composition of the present invention. It is desirable to be included in the amount. When the silane coupling agent (a2) is contained in the above amount in the epoxy resin composition, the adhesion between the film formed from the composition and the substrate surface is improved, and it is immersed in water for a long period of time. However, there is no peeling of the film, and it is possible to effectively prevent pitting corrosion, crevice corrosion, dissimilar metal contact corrosion, and stress corrosion of metal substrates (especially stainless steel substrates). These effects are prominent when a silane coupling agent containing an epoxy group is added.
[0060]
[Table 1]

[0061]
Liquid hydrocarbon resin
The main component (A) used in the present invention preferably further contains a liquid hydrocarbon resin.
[0062]
Such a liquid hydrocarbon resin (liquid petroleum resin) is a liquid hydrocarbon resin that is liquid at room temperature (temperature of 15 to 25 ° C.) and has a viscosity in the range of 500 to 400,000 mPa · s / 25 ° C. Specific examples of such liquid hydrocarbon resins include aliphatic hydrocarbons (C9 petroleum resins), aromatic hydrocarbons (C5 petroleum resins), chroman resins, xylene resins, toluene resins, and modified products thereof. Such as things.
[0063]
In the present invention, such liquid hydrocarbon resins can be used alone or in combination of two or more. Thus, when using in combination of 2 or more types of liquid hydrocarbon resin, the said molecular weight of liquid hydrocarbon resin is shown by the average value.
[0064]
Among the liquid hydrocarbon resins, it is necessary to have good compatibility with the epoxy resin, and preferably, aromatic hydrocarbon (C5 petroleum resin), xylene resin, or toluene resin is used. desirable.
[0065]
The average molecular weight and the like of such a liquid hydrocarbon resin are not generally determined depending on the coating curing conditions (eg, normally dry coating or baking coating) of the obtained paint, but the number average molecular weight is usually 150 to 720 having a viscosity of 30 to 700,000 mPa · s / 25 ° C. is used.
[0066]
The typical liquid hydrocarbon resin is specifically,
Examples of aliphatic hydrocarbons (C9 petroleum resin) include Nesiles EPX-L, Nebuchem NL-10, Nebuchem NL-20, Nebuchem NL-30, Nesiles EPX-T6 (trade names, all manufactured by Nevcin Polymers co.), Etc. Can be mentioned.
[0067]
Examples of the aromatic hydrocarbon (C5-based petroleum resin) include Maruka Clear H and Maruka Clear V (trade names, both manufactured by Maruzen Petroleum Co., Ltd.).
[0068]
Examples of the xylene resin include Nicanol DS, LLL, LL, L, and H (trade names, all manufactured by Mitsubishi Gas Chemical Co., Ltd.) and Hysol SASLH (trade names, manufactured by Shin Nippon Petrochemical Co., Ltd.). it can.
[0069]
Examples of the chroman resin include Escron L-5 and L-20 (trade names, both manufactured by Nippon Steel Chemical Co., Ltd.).
[0070]
Examples of the toluene resin include Epoxy L (trade name, manufactured by Anchor Chemical Co., Ltd.).
[0071]
In the present invention, these liquid hydrocarbon resins may be used alone or in combination.
[0072]
Color pigment, extender pigment
In a further preferred embodiment of the present invention, among the color pigment and / or extender pigment contained in the main component (A), the color pigment is not particularly limited, and conventionally known color pigments such as carbon black, titanium dioxide, valve Examples thereof include inorganic pigments such as handles, iron oxide, iron hydroxide and ultramarine blue, and organic pigments such as cyanine blue and cyanine green. A color pigment can be used individually by 1 type or in combination of 2 or more types.
[0073]
The extender pigment is a conventionally known extender pigment such as precipitated barium sulfate, calcium carbonate, potassium feldspar, kaolin, alumina white, clay, talc, bentonite, magnesium carbonate, barium carbonate, silica fine powder, mica powder. Glass flakes, stainless steel flakes, aluminum flakes, plastic flakes and the like. As the extender used in the present invention, precipitated barium sulfate, calcium carbonate, potassium feldspar, mica powder, and glass flakes are preferably used. The extender pigments can be used alone or in combination of two or more.
[0074]
When the epoxy resin composition of the present invention is used in a spent nuclear fuel storage pool, it is preferable to use titanium dioxide as the coloring pigment and fine silica powder as the extender pigment. The reason for being limited to such a pigment is that the amount of the low melting point metal or halogen eluted into water is limited.
[0075]
The coloring pigment and / or extender pigment is usually used in an amount of 5 to 80 parts by weight, preferably 20 to 70 parts by weight, and more preferably 40 to 60 parts by weight with respect to 100 parts by weight of the main component (A).
[0076]
Other ingredients
The main component (A) used in the present invention includes, in addition to the liquid epoxy resin (a1), the liquid hydrocarbon resin, and the color pigment and / or extender pigment, as other components, a fiber material, anti-sagging and settling prevention An agent, a surfactant described in JP-A-2-298563, a rust preventive pigment, and the like can be appropriately added.
[0077]
(Fiber material)
Examples of the fiber material include asbestos, wollastonite, sepiolite, potassium titanate whisker, calcium silicate whisker, basic magnesium sulfate, vegetable fiber, glass fiber, carbon fiber, and synthetic fiber, preferably wollastonite, Sepiolite and potassium titanate whiskers are used.
[0078]
Such fiber materials include NYAD 1250 (Wollastonite; manufactured by NYCO Minerals Inc), Milcon MS-2-2 (Sepiolite; manufactured by Showa Mining Co., Ltd.), Tismo-D (potassium titanate whisker; Otsuka Chemical Co., Ltd.) ))).
[0079]
The fiber material may be contained in the main component (A) (100% by weight), for example, in an amount of 0.1 to 10% by weight.
[0080]
(Anti-sagging / anti-settling agent)
Examples of the anti-sagging / anti-settling agent include organic viscosity Al, Ca, Zn stearate salts, lecithin salts, alkyl sulfonate salts, polyethylene wax, amide wax, hydrogenated castor oil wax, polyamide wax And mixtures thereof, synthetic fine powder silica, oxidized polyethylene wax, and the like. Polyamide wax, synthetic fine powder silica, oxidized polyethylene wax, and organic viscosity system are preferably used.
[0081]
Examples of such anti-sagging and anti-settling agents include “DISPARON 305” and “DISPARON 4200-20” manufactured by Enomoto Kasei Co., Ltd., “DISPARON 6650”, and “ASAT-250F” manufactured by Ito Seiyaku Co., Ltd. ”And the like are listed on the market.
[0082]
The anti-sagging / anti-settling agent may be contained in the main component (A) (100% by weight), for example, in an amount of 0.1 to 10% by weight.
[0083]
(Surfactant)
As the surfactant, surfactants described in JP-A-2-298563 can be used. Specifically, the following general formulas (1), (2), (3), (4), (5 )
[0084]
[Chemical 1]

[0085]
(In the formula, M represents hydrogen, a metal, or a basic nitrogen-containing compound.)
A surfactant having at least one acid group represented by the formula (or a salt thereof) is used.
[0086]
The surfactant may be contained in the main component (A) (100% by weight), for example, in an amount of 1 to 5% by weight.
[0087]
(Anti-rust pigment)
Examples of the rust preventive pigment include chromic acid, molybdic acid, phosphoric acid, boric acid, ferrite, and lead acid pigments. In the present invention, it is preferable to use a phosphate pigment, and examples thereof include phosphate zinc phosphate and aluminum tripolyphosphate.
[0088]
Examples of such rust preventive pigments include LF Bowsey 2P-DL (manufactured by Kikuchi Color Co., Ltd.) and K-White # 82 (manufactured by Teika Co., Ltd.).
[0089]
The rust preventive pigment may be contained in an amount of, for example, 5 to 30% by weight with respect to 100% by weight of the color pigment and / or extender.
[0090]
  In addition, since the epoxy resin composition of the present invention can be painted in the air and water (including in seawater),Epoxy resin compositionThe main ingredient component (A) contained in is substantially free of a solvent used for dissolving the resin component. If the epoxy resin composition of the present invention is used only for coating in the atmosphere, there are no practical problems (such as poor solvent removal from the film and problems in film formation). It is also possible to add the above-mentioned solvent to the main component (A), and it is also possible to contain a large amount of solvent if it is coated with a thin film or applied several times with a thin film to form a thick film.
[0091]
Such a main ingredient component (A) can be obtained by blending the above components in the above amounts and stirring and kneading with a three roll or high speed disper.
[0092]
<Curing agent component (B)>
  The epoxy resin composition of the present invention comprises the main component (A) and the curing agent component (B), and the curing agent component (B)NContains a system curing agent (b1). Furthermore, it is also preferable that liquid hydrocarbon resin is contained.
[0093]
  AmiNThe system curing agent (b1) is Mannich-modified amines (b1-1) and / or aliphatic polyamines (b1-2) formed by a Mannich condensation reaction of phenols, formalin, and an amine compound. It is preferable.
[0094]
In a further preferred embodiment of the present invention, the curing agent component (B) contains a color pigment and / or an extender pigment.
[0095]
Mannich modified amines ( b1-1 )
The Mannich-modified amines (b1-1) are formed by a Mannich (dehydration) condensation reaction of phenols, formaldehyde, and an amine compound.
Examples of the phenols include unsaturated substituent-containing phenols and saturated substituent-containing phenols.
[0096]
The unsaturated substituent-containing phenol includes at least one monohydroxyphenyl group in the molecule and a part of the phenyl group hydrogen, that is, one in which 1 to 5 hydrogen atoms are substituted with an unsaturated hydrocarbon group, etc. Is mentioned.
[0097]
Examples of the unsaturated hydrocarbon group include an alkylene group having about 1 to 10 carbon atoms and a phenyl group containing the alkylene group.
[0098]
Specific examples of the unsaturated substituent-containing phenol include cardanol, isopropenylphenol, diisopropenylphenol, butenylphenol, isobutenylphenol, cyclohexenylphenol,
Monostyrenated phenol (C₆H_Five-CH = CH-C₆H_Four-OH),
Distyrenated phenol ((C₆H_Five-CH = CH)₂-C₆H_Three-OH),
Etc.
[0099]
Such Mannich-modified amines (b1-1) are usually 10 to 40 in 100% by weight of the curing agent component (B).weight%, Preferably 20-30weight% Is preferably included.
[0100]
More specifically, examples of the alkylphenol include monohydric phenols such as methylphenol (o, m, p-cresol), ethylphenol, butylphenol, tertiary butylphenol, octylphenol, nonylphenol, dodecylphenol, dinonylphenol,
Examples of the halogenated phenol include monohydric phenols such as chlorophenol.
[0101]
Of these, monovalent mononuclear phenols are preferred.
[0102]
The amine compound may be any of aliphatic, alicyclic, aromatic, heterocyclic and the like.
[0103]
Examples of the aliphatic amine compound include alkylene polyamines, polyalkylene polyamines, other aliphatic polyamines, and the like.
More specifically, examples of the alkylene polyamine include a formula: H₂N-R¹-NH₂(R¹: A divalent hydrocarbon group having 1 to 12 main carbon atoms which may have one or more hydrocarbon group side chains having 1 to 10 carbon atoms), for example, methylenediamine, ethylenediamine, 1 , 2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1, 9-diaminononane, 1,10-diaminodecane and the like are used.
[0104]
Examples of the polyalkylene polyamine include the formula: H₂N- (C_mH_2mNH)_nH (m: an integer of 1 to 10, n: 2 to 10, preferably an integer of 2 to 6), and more specifically, for example, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, Examples include tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecane, and trimethylhexamethylenediamine.
[0105]
Examples of other aliphatic polyamines include tetra (aminomethyl) methane, tetrakis (2-aminoethylaminomethyl) methane, 1,3 as described in JP-B-49-48480, column 24, and the like. -Bis (2'-aminoethylamino) propane, triethylene-bis (trimethylene) hexamine, bis (3-aminoethyl) amine, bishexamethylenetriamine [H₂N (CH₂)_nNH (CH₂)_nNH₂, N = 6], and the like.
[0106]
More specifically, examples of the alicyclic amines include 1,4-cyclohexanediamine, 4,4′-methylenebiscyclohexylamine, 4,4′-isopropylidenebiscyclohexylamine, norbornadiamine, bis ( Aminomethyl) cyclohexane, diaminodicyclohexylmethane, isophoronediamine, mensendiamine (MDA) and the like.
[0107]
Aromatic amines include bis (aminoalkyl) benzene, bis (aminoalkyl) naphthalene, aromatic polyamine compounds having two or more primary amino groups bonded to the benzene ring, and other aromatic polyamines. Etc.
[0108]
More specifically, examples of the aromatic amines include bis (cyanoethyl) diethylenetriamine, o-xylylenediamine, m-xylylenediamine (MXDA), p-xylylenediamine, phenylenediamine, naphthylenediamine, Diaminodiphenylmethane, diaminodiethylphenylmethane,
2,2-bis (4-aminophenyl) propane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 2,2 ′ -Dimethyl-4,4'-diaminodiphenylmethane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, bis (Aminomethyl) naphthalene, bis (aminoethyl) naphthalene and the like can be mentioned.
[0109]
More specifically, examples of the heterocyclic amines include N-methylpiperazine [CH._Three-N (CH₂CH₂)₂NH], morpholine [HN (CH₂CH₂)₂O], 1,4-bis- (8-aminopropyl) -piperazine, piperazine-1,4-diazacycloheptane, 1- (2'-aminoethylpiperazine), 1- [2 '-(2 "- Aminoethylamino) ethyl] piperazine, 1,11-diazacycloeicosane, 1,15-diazacyclooctacosane and the like.
[0110]
Other examples of amine compounds that can be used in the present invention include aromatic amines described in JP-B No. 49-48480, page 12, column 24, line 43 to page 14, column 28, line 25 ( Amine compounds) can also be used.
[0111]
Other examples include diethylaminopropylamine and polyetherdiamine.
[0112]
In the present invention, these amine compounds can be used alone or in combination of two or more.
[0113]
Among these amine compounds, the alkylene polyamines and polyalkylene polyamines belonging to the aliphatic group are preferable, and ethylene diamine and diethylene polyamine are more preferable.
[0114]
In the Mannich dehydration condensation reaction, for example, cardanol, which is a kind of phenols, formaldehyde, and xylylenediamine as an amine compound may be theoretically used in equimolar amounts. Formaldehyde is used in an amount of 0.5 to 2.5 mol, and an amine compound is used in an amount of 0.5 to 2.5 mol with respect to 1 mol, at a temperature of about 50 to 180 ° C. for about 3 to 12 hours. What is necessary is just to heat-hold.
[0115]
Among the Mannich-modified amines (b1-1) obtained by subjecting an unsaturated substituent-containing phenol, formaldehyde, and an amine compound to a Mannich condensation reaction, cardanol of the unsaturated substituent-containing phenol, formaldehyde, and Mannich-modified amine obtained by reacting an amine compound with the above-mentioned alkylene polyamine or polyalkylene polyamine is preferable.
[0116]
These Mannich-modified amines (b1-1) are usually N.I. V. It is preferable that the content is adjusted to 40 to 100% and the amine value (mgKOH / g) is in the range of 300 to 500 because a film excellent in adhesion to a substrate, water resistance, and corrosion resistance can be formed.
[0117]
As such Mannich-modified amines (b1-1), specifically,
Made by Air Products: Ancamine 2432 (NV 43.5%, amine number 387), Ancamine 2089M (NV 100%, amine number 368),
Made by Cognis Japan: Versamine F20 (NV 100%, amine number 400-480), Versamine I-368 (NV 100%, amine number 370-400), Versamine M-1 (NV 100%, amine number 375-425),
Made by Shell: EpiCure 3549 (NV100%), EpiCure 3378 (NV74.5%),
Witco: TL0712 (NV94.3%, amine number 705),
Asahi Denka Co., Ltd .: Adeka Hardener EH342M (NV 40.2%, amine number 307), Adeka Hardener EH342M17 (NV 33.3%, Amine number 386), Adeka Hardener EH350 (NV 52.8%, Amine number 385), Adeka Hardener EH351 (NV 46.9%, amine number 306),
Sanwa Chemical Industry Co., Ltd .: Sanmide W-3000 (NV100%, amine value 340), Sunmide W-1000 (NV100%, amine value 340), Sunmide W-500 (NV100%, amine value 280), Sunmide CX- 102 (NV89.8%, amine number 288),
Daito Sangyo Co., Ltd .: Daitokural SK900FCB (NV 100%, amine value 385),
Dainippon Ink & Chemicals, Inc .: Lacamide V6-221 (NV 100%, amine number 420)
Etc. In the present invention, these Mannich-modified amines (b1-1) can be used alone or in combination of two or more.
[0118]
In the present invention, it is desirable that the Mannich-modified amines (b1-1) are Mannich-modified amines that are hardly soluble or insoluble in water. If the Mannich-modified amine (b1-1) is easily soluble in water, it becomes difficult to apply the resulting epoxy resin composition to the wet surface.
[0119]
Such Mannich-modified amines (b1-1) are usually contained in an amount of 10 to 40% by volume, preferably 20 to 30% by volume, in 100% by weight of the curing agent component (B). preferable.
[0120]
When the Mannich-modified amines (b1-1) are contained in the curing agent component (B) in the amounts described above, the epoxy resin composition according to the present invention has improved curing speed and low-temperature curability.
[0121]
Aliphatic polyamines ( b1-2 )
Examples of the aliphatic polyamines (b1-2) contained in the curing agent component (B) together with the Mannich-modified amines (b1-1) include alkylene polyamines, polyalkylene polyamines, and other aliphatic polyamines. Etc.
[0122]
Specifically, as the alkylene polyamine, for example, the formula: H₂N-R¹-NH₂(R¹: A divalent hydrocarbon group having 1 to 12 main carbon atoms which may have one or more hydrocarbon group side chains having 1 to 10 carbon atoms), for example, methylenediamine, ethylenediamine, 1 , 2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1, 9-diaminononane, 1,10-diaminodecane and the like are used.
[0123]
Examples of the polyalkylene polyamine include the formula: H₂N- (C_mH_2mNH)_nH (m: an integer of 1 to 10, n: 2 to 10, preferably an integer of 2 to 6), and more specifically, for example, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, Examples include tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecane, and trimethylhexamethylenediamine.
[0124]
Examples of other aliphatic polyamines include tetra (aminomethyl) methane, tetrakis (2-aminoethylaminomethyl) methane, 1,3 as described in JP-B-49-48480, column 24, and the like. -Bis (2'-aminoethylamino) propane, triethylene-bis (trimethylene) hexamine, bis (3-aminoethyl) amine, bishexamethylenetriamine [H₂N (CH₂)_nNH (CH₂)_nNH₂, N = 6], and the like.
[0125]
In the present invention, these aliphatic polyamines (b1-2) can be used alone or in combination of two or more.
[0126]
These aliphatic polyamines (b1-2) are usually N.I. V. It is preferable that the content is adjusted to 40 to 100% and the amine value (mgKOH / g) is in the range of 300 to 500 because a film excellent in adhesion to a substrate, water resistance, and corrosion resistance can be formed. The active hydrogen equivalent (g / equiv) of the amino group of such aliphatic polyamines (b1-2) is not generally determined, but those of 80 to 250 are usually used.
[0127]
Specific examples of the aliphatic polyamines (b1-2) include “ACI Hardener (R) K-39” (manufactured by PTI Japan Ltd. = IBPTR Japan Ltd.), “Surwet R”, “Ancamine 1784”. (Both manufactured by Air Products Japan Co., Ltd.), “ADEKA HARDNER EH240”, “ADEKA HARDNER EH270” (all manufactured by Asahi Denka Co., Ltd.), and the like. In the present invention, these aliphatic polyamines may be used alone or in combination of two or more.
[0128]
In the present invention, the aliphatic polyamines (b1-2) are desirably aliphatic polyamines that are hardly soluble or insoluble in water. If the aliphatic polyamines (b1-2) are easily soluble in water, it is difficult to apply the resulting epoxy resin composition to the wet surface.
[0129]
The aliphatic polyamines (b1-2) are usually contained in an amount of 10 to 40% by weight, preferably 20 to 30% by weight, in 100% by weight of the curing agent component (B).
[0130]
The epoxy resin composition of the present invention contains the aliphatic polyamines (b1-2) having room temperature curing properties in the above amounts or the Mannich-modified amines (b1-1) in the above amounts. The curing rate can be adjusted, and the coating composition corresponding to the use conditions in air or water can be prepared. Furthermore, by containing the above (b1-1), (b1-2) and the resin component (liquid epoxy resin (a1) and liquid hydrocarbon resin) in the above amounts, adhesion to a substrate, It has excellent water resistance and can effectively prevent corrosion of the base material, and in particular, effectively prevents pitting corrosion, crevice corrosion, dissimilar metal contact corrosion, and stress corrosion of metal base materials (especially stainless steel base materials). An anticorrosion film that can be formed can be formed.
[0131]
Liquid hydrocarbon resin
The curing agent component (B) of the present invention preferably contains a liquid hydrocarbon resin (liquid petroleum resin) as described above.
[0132]
As this liquid hydrocarbon resin, the same liquid hydrocarbon resin contained in the main component (A) can be used.
[0133]
In the present invention, the liquid hydrocarbon resin is usually 5 to 70 in a total amount of 100% by weight of (a1), (a2), (b1) and the liquid hydrocarbon resin contained in the epoxy resin composition. It is desirable that it is contained in an amount of 10% by weight, preferably 10 to 50% by weight.
[0134]
Furthermore, the liquid hydrocarbon resin is desirably contained in the epoxy resin composition (100 wt%) of the present invention in an amount of 1 to 50 wt%, preferably 5 to 30 wt%.
[0135]
By forming the liquid hydrocarbon resin into the epoxy resin composition of the present invention in the above amount, a film having excellent adhesion to the substrate, water resistance, and corrosion resistance is formed on the surface of the substrate. Can do.
[0136]
Color pigment, extender pigment
In a further preferred embodiment of the present invention, the curing agent component (B) may be blended with the same pigments and extender pigments used for the main component (A).
[0137]
Further, the color pigment and / or extender pigment is usually 5 to 80 parts by weight, preferably 20 to 70 parts by weight, and more preferably 40 to 60 parts by weight with respect to 100 parts by weight of the curing agent component (B). Used.
[0138]
The total capacity of the color pigment and extender pigment contained in the main component (A) and / or the curing agent component (B) is 10 to 50% by volume in 100% by volume of the epoxy resin composition of the present invention, preferably It is desirable that it is contained in an amount of 15 to 30% by volume, more preferably 20 to 25% by volume.
[0139]
When the epoxy resin composition of the present invention contains the color pigment and the extender pigment in the above amounts, the coating workability is excellent even if the composition is a solventless type. Furthermore, the film stress caused by curing and shrinkage of the coated film is relieved, and the adhesive force does not decrease.
[0140]
Other ingredients
The curing agent component (B) used in the present invention includes the Mannich-modified amines (b1-1), the aliphatic polyamines (b1-2), and other components besides the color pigment and / or extender pigment. , Fiber substances, anti-sagging / anti-settling agents, surfactants described in JP-A-2-298563, polycarboxylic acids or salts thereof described in JP-A-2-251579, rust preventive pigments and the like can be appropriately added.
Such fiber materials, anti-sagging agents, anti-settling agents, surfactants described in JP-A-2-298563, polycarboxylic acids or salts thereof described in JP-A-2-251579 were used for the main component (A). Similar ones can be used.
[0141]
The amount of each component added is
The fiber material may be contained in the curing agent component (B), for example, in an amount of 0.1 to 10% by weight,
The anti-sagging / anti-settling agent may be contained in the curing agent component (B), for example, in an amount of 0.1 to 10% by weight,
The surfactant as described above may be contained in the curing agent component (B), for example, in an amount of 1 to 5% by weight,
The polycarboxylic acid or salt thereof as described above may be contained in the curing agent component (B) in an amount of, for example, 1 to 5% by weight,
The rust preventive pigment may be contained in the curing agent component (B) in an amount of, for example, 5 to 30% by weight,
The curing agent component (B) used in the present invention is obtained by blending the above components in the above amounts and stirring and kneading with a three roll or high speed disper.
[0142]
[Epoxy resin composition]
As described above, the epoxy resin composition according to the present invention comprises (A) a main agent component and (B) a curing agent component,
The main agent component (A) contains the liquid epoxy resin (a1) and the silane coupling agent (a2), and the curing agent component (B) contains the amine curing agent (b1),
The main component (A) and / or the curing agent component (B) contains a liquid hydrocarbon resin.
[0143]
The equivalent ratio represented by the epoxy equivalent (g / equiv) in the main component (A) / active hydrogen equivalent (g / equiv) of the amino group in the curing agent component (B) is 0.5-2. It is desirable that the amount is 0, preferably 0.8 to 1.5, and more preferably 0.9 to 1.2.
[0144]
In the epoxy resin composition of the present invention, since the main component (A) and the curing agent component (B) are blended in such a range, the adhesion to the base material, water resistance, and corrosion resistance are excellent. An anticorrosion film capable of preventing pitting corrosion, crevice corrosion, dissimilar metal contact corrosion, and stress corrosion of a metal substrate (particularly a stainless steel substrate) can be formed.
[0145]
Furthermore, it also acts as an adhesive, and a stainless steel plate can be adhered to the surface of the film, so that local corrosion can be stably prevented for a long period of time, and corrosion resistance can be imparted.
[0146]
Such an epoxy resin composition of the present invention is usually in a two-part form of the main component (A) containing an epoxy resin and the curing agent component (B) containing a curing agent component. , Each stored in a separate container.
[0147]
The epoxy resin composition of the present invention is used by mixing immediately before use even when coating in the air or in water.
[0148]
In addition, as a hardening | curing agent for epoxy resins, when using the hardening | curing agent modified | denatured so that it may not react with an epoxy resin component during storage, a bisphenol-type epoxy resin composition can be used as a 1 liquid type. Examples of the modified curing agent include ketimine type amine block curing agents. Specific examples of ketimine type amine block curing agents include EpiCure H30 (manufactured by Japan Epoxy Resin Co., Ltd.), Adeka Hardener EH-235R (manufactured by Asahi Denka Kogyo Co., Ltd.), and the like. The ketimine type amine block curing agent may be used in combination with Mannich-modified amines (b1-1) and / or aliphatic polyamines (b1-2) in a two-pack type epoxy resin composition. it can.
[0149]
As shown below, the epoxy resin composition according to the present invention is an anticorrosion composition capable of forming a film having excellent anticorrosion properties on the surface of the substrate, particularly an anticorrosion composition for a stainless steel substrate, and a stainless steel plate having a stainless steel structure. It is useful as an adhesive composition to be attached to the surface of an object.
[0150]
[Anti-corrosion coating, substrate with anti-corrosion coating, anti-corrosion method, etc.]
The anticorrosive film (layer) of the present invention is formed from the epoxy resin composition, and the film thickness after curing is not particularly limited, but is preferably 200 to 5000 μm, preferably 500 to 2000 μm.
[0151]
When the film thickness of the anticorrosion film (layer) is within the above range, a film excellent in anticorrosion property can be effectively formed on the substrate surface.
[0152]
Moreover, the base material surface with the anticorrosion film | membrane which concerns on this invention is coat | covered with the anticorrosion film | membrane of this invention as mentioned above. Examples of such a substrate include steel and non-ferrous metals (such as zinc, aluminum, and stainless steel). In the present invention, it is useful to use stainless steel. Therefore, the anticorrosion film (layer) of the present invention has excellent adhesion to the substrate, preferably a stainless steel substrate, excellent water resistance, and prevents pitting corrosion, crevice corrosion, dissimilar metal contact corrosion, and stress corrosion. be able to.
[0153]
When such an anticorrosion film is formed in the air, specifically, the epoxy resin composition is prepared after applying a base preparation such as polishing the surface of a stainless steel substrate (eg, SUS403) with sandpaper. It is formed by coating with a brush, a roller, a spatula, a trowel or the like, and the composition is cured. In addition, when the anticorrosion film is formed in water, for example, in repair coating or maintenance coating, the epoxy resin composition is applied to the repaired part by brush, spatula, iron, etc., and the composition is cured. It is formed.
[0154]
According to the anticorrosion method of the present invention, a film having the above effects can be formed, and pitting corrosion, crevice corrosion, dissimilar metal contact corrosion, and stress corrosion of the substrate can be prevented.
[0155]
In addition, since the composition of the present invention can form a film with excellent performance as described above on the surface of the base material, the seawater desalination apparatus, a place where maintenance of marine structures is difficult, a dam or a sluice gate. Can be used for piping, storage tanks, water storage tanks, spent nuclear fuel storage pools, etc., around plants that use seawater, river water, and industrial water as cooling water, and with anticorrosive coatings that cause the corrosion It is also possible to repair coat the surface of the substrate.
[0156]
In addition, the epoxy resin composition of the present invention forms an anticorrosive coating at a welded portion or gap in stainless steel to prevent local corrosion of the stainless steel base material, and also acts as an adhesive. By attaching a stainless steel plate to the coating surface, local corrosion can be stably prevented for a long period of time, and corrosion resistance can be imparted.
[0157]
Such a repair method is not particularly limited. Specifically, as described above, the epoxy resin composition of the present invention is applied to the surface of a stainless steel substrate having a welded portion (weld line) or a gap, and is uncured. A stainless steel plate is adhered to the surface of the coating film. Furthermore, you may apply | coat the epoxy resin composition of this invention on this.
[0158]
Although this repair method is not particularly limited as long as it is a stainless steel structure, specifically, it is performed on a water tank, a water tank, a spent nuclear fuel storage pool, or the like. Among these, the spent nuclear fuel storage pool tends to cause local corrosion when there are welds (welding lines) or gaps on the surface of the base material inside the storage pool. Therefore, according to the repair method using the epoxy resin composition of the present invention, local corrosion can be stably prevented for a long period of time, and corrosion resistance can be imparted.
[0159]
When the composition of the present invention is applied, dried, and cured, for example, the epoxy group in the epoxy resin contained in the main component (A) is ring-opened, and the epoxy oxygen (O) is a hydroxyl group (—OH). In addition, the carbon at the end of the molecule forming the epoxy group is the amino group “—NH” in the curing agent.₂It is presumed that it is bonded to the curing agent through a “—NH—” bond or the like.
[0160]
【The invention's effect】
According to the epoxy resin composition of the present invention, it has excellent adhesion to a substrate, water resistance, and corrosion resistance, and in particular, pitting corrosion, crevice corrosion, dissimilar metal contact corrosion, stress on metal substrates (especially stainless steel substrates). An anticorrosion film that can prevent corrosion can be formed.
[0161]
This epoxy resin composition can be applied even in water, and has a coating with excellent characteristics as described above. Desalination equipment, places where maintenance of offshore structures is difficult, around dam and sluice gates, seawater and rivers It can be suitably used for anticorrosion applications of base materials such as pipes for plants using water or industrial water as cooling water, water tanks, water storage tanks, spent nuclear fuel storage pools and the like.
[0162]
In addition, the epoxy resin composition of the present invention forms an anticorrosive coating at a welded portion or gap in stainless steel to prevent local corrosion of the stainless steel base material, and also acts as an adhesive. By attaching a stainless steel plate to the coating surface, local corrosion can be stably prevented for a long period of time, and corrosion resistance can be imparted.
[0163]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
[0164]
The raw materials used in this example are shown in Table 2.
[0165]
Examples 1-11, Comparative Examples 1-5
<Preparation method of main agent / curing agent and preparation method of epoxy resin composition>
1. The liquid resin contained in the main ingredient component shown in Table 3 and Table 4 is blended in a container, heated to 50 ° C. with stirring, and then other raw materials used are kneaded with a high-speed disper. Examples and Comparative Examples The main agent used in was prepared.
[0166]
In Comparative Example 1 and Comparative Example 3, Epicoat 1001 and Neopolymer E-100, which are solid resins, were each added in small amounts while stirring with a disper while stirring xylene heated to 50 ° C., and then blended.
[0167]
2. The liquid resin contained in the curing agent shown in Table 2 and Table 3 is heated to 50 ° C. while stirring, and other raw materials used are kneaded with a high-speed disperser, and the curing agents used in the examples and comparative examples are as follows. Prepared.
[0168]
3. Immediately before the test, the main agent and the curing agent prepared by the above method were used after mixing with a gold spatula at a mixing ratio indicated by a small amount.
<Test method: Preparation of test plate and test plate>
1. A stainless steel plate of SUS304 is polished in advance with Scotch Bright industrial pad No. 7447, and finished to a surface roughness Ra of 0.3 to 0.6 μm. The size of the stainless steel plate was 70 × 150 × 3 mm for adhesive strength measurement and 50 × 200 × 0.3 mm for the bending resistance test.
[0169]
2. At both ends in the longitudinal direction of the stainless steel plate, a 1 mm thick 3 mm × 150 mm vinyl chloride plate is fixed with a double-sided adhesive tape (double-sided adhesive tape No. 5015 manufactured by Nitto Denko).
[0170]
3. The epoxy resin compositions of Examples and Comparative Examples were scraped on the 1 mm-thick vinyl chloride plate attached as described above using a gold spatula in the atmosphere and in tap water left for a whole day and night. Then, it was applied to the surface of the stainless steel plate so that the film thickness was about 1 mm. It was cured for 1 week under the respective coating conditions.
<Evaluation method>
A. Bond strength measurement with stainless steel
The adhesive strength was measured according to the adhesion measuring procedure by the pull-off method specified in JIS K 5600-5-7 7.3.2. Use a 20 mm diameter cylindrical jig for adhesion measurement, roughen the coated surface with # 80 sandpaper, adhere the adhesion measurement jig with an epoxy resin adhesive, and pull it at 2 mm per minute. The adhesive strength with stainless steel was measured.
B. Bending resistance
1. The bending resistance was measured using the bending resistance measuring apparatus 10 shown in the schematic diagram of FIG. As shown in the figure, the test plate 20 is placed on the two support bases 12 and 12 with the coating surface 22 facing downward, and a precision universal testing machine (Autograph AGS-1000A, manufactured by Shimadzu Corporation) not shown is installed. In use, the indenter 14 is lowered at 10 mm per minute. The indenter 14 is further lowered by 10 mm from the position where the indenter 14 hits the test plate 20.
[0171]
2. After the indenter 14 was lowered by 10 mm, the indenter 14 was immediately raised to observe whether the coating surface 22 was cracked.
[0172]
The results are shown in Table 5.
[0173]
[Table 2]

[0174]
[Table 3]

[0175]
[Table 4]

[0176]
[Table 5]

[Brief description of the drawings]
FIG. 1 is a schematic view of a measuring apparatus used in a bending resistance test in Examples.
[Explanation of symbols]
10 Bending resistance measuring device
12 Support stand
14 Indenter
20 test plate
22 Paint surface
R₁    Tip radius of indenter 14
R₂    Curvature radius of support base 12

Claims (39)

In the epoxy resin composition comprising (A) a main agent component and (B) a curing agent component,
The main agent component (A) contains a liquid epoxy resin (a1) and a silane coupling agent (a2), the curing agent component (B) contains an amine curing agent (b1),
The main component (A) and / or the curing agent component (B) contains a liquid hydrocarbon resin,
The amine curing agent is a Mannich-modified amine (b1-1) formed by an unsaturated substituent-containing phenol or a saturated substituent-containing phenol, formalin, and an amine compound, and / or an aliphatic polyamine. (B1-2),
The silane coupling agent (a2) is contained in an amount of 0.1 to 15% by weight in 100% by weight of the epoxy resin composition,
The liquid hydrocarbon resin is contained in the epoxy resin composition (100 wt%) in an amount of 1 to 50 wt%,
The Mannich-modified amine (b1-1) is contained in an amount of 10 to 40% by weight in 100% by weight of the curing agent component (B),
The aliphatic polyamine (b1-2) is contained in an amount of 10 to 40% by weight in 100% by weight of the curing agent component (B),
The epoxy equivalent of the liquid epoxy resin (a1) is in the range of 150 to 300,
The Mannich modified amine (b1-1) has an amine value (mgKOH / g) in the range of 300 to 500;
The active hydrogen equivalent (g / equiv) of the amino group of the aliphatic polyamine (b1-2) is 80 to 250,
The equivalent ratio represented by epoxy equivalent (g / equiv) in the main component (A) / active hydrogen equivalent (g / equiv) of amino group in the curing agent component (B) is 0.5-2. The component (A) and the component (B) are contained so as to be 0.0.
An anticorrosive composition for a stainless steel substrate, comprising an epoxy resin composition. The Mannich-modified amine (b1-1) is
A compound containing at least one monohydroxyphenyl group in the molecule and having 1 to 5 hydrogen atoms substituted with an unsaturated hydrocarbon group, phenol, divalent mononuclear phenol, divalent polynuclear phenol, alkylphenol (alkyl group) 1 to 10), halogenated phenol, alkoxyphenol (1 to 10 carbon atoms of alkoxy group), 2,2-di (p-hydroxyphenyl) -propane or di (p-hydroxyphenyl) -methane,
Formalin,
The anticorrosive composition for a stainless steel substrate according to claim 1, which is a Mannich-modified amine formed by a Mannich condensation reaction with an amine compound.   The anticorrosion composition for a stainless steel substrate according to claim 1 or 2, wherein the aliphatic polyamine (b1-2) has an amine value (mgKOH / g) in the range of 300 to 500.   The said main ingredient component (A) and / or hardening | curing agent component (B) contain a color pigment and / or an extender, The anticorrosion composition for stainless steel base materials in any one of Claims 1-3 characterized by the above-mentioned. .   The equivalent ratio represented by epoxy equivalent (g / equiv) in the main component (A) / active hydrogen equivalent (g / equiv) of amino group in the curing agent component (B) is 0.8 to 1. The anticorrosive composition for a stainless steel substrate according to any one of claims 1 to 4, wherein (A) and (B) are contained so as to be .5.   The epoxy resin composition comprises the silane coupling agent (a2) in an amount of 0.5 to 5% by weight in 100% by weight of the composition. The anticorrosion composition for stainless steel bases in any one.   The stainless steel according to any one of claims 1 to 6, wherein the colored pigment and / or the extender pigment is contained in an amount of 10 to 50% by volume in 100% by volume of the epoxy resin composition. Anticorrosive composition for base material.   The stainless steel according to any one of claims 1 to 7, wherein the colored pigment and / or the extender pigment is contained in an amount of 15 to 30% by volume in 100% by volume of the epoxy resin composition. Anticorrosive composition for base material.   The color pigment and / or extender pigment is contained in an amount of 5 to 80 parts by weight with respect to 100 parts by weight of the curing agent component (B). Anti-corrosion composition for stainless steel substrate.   The liquid hydrocarbon resin is contained in an amount of 5 to 70% by weight in 100% by weight of the total amount of (a1), (a2), (b1) and the liquid hydrocarbon resin contained in the epoxy resin composition. The anticorrosive composition for a stainless steel substrate according to any one of claims 1 to 9, wherein   The said main ingredient component (A) does not contain a solvent, The anticorrosion composition for stainless steel base materials in any one of Claims 1-10 characterized by the above-mentioned.   The anticorrosion composition for a stainless steel substrate according to any one of claims 1 to 11, wherein the anticorrosion composition is for underwater coating or wet surface coating.   An anticorrosion film formed from the anticorrosion composition for a stainless steel substrate according to any one of claims 1 to 12.   A stainless steel substrate with an anticorrosion film, wherein the base material surface is coated with the anticorrosion film according to claim 13.   A stainless steel structure with an anticorrosion film, wherein the surface of the stainless steel structure is coated with the anticorrosion film according to claim 13.   The stainless steel structure with an anticorrosion film according to claim 15, wherein the stainless steel structure is a water storage tank or a water storage tank.   A repaired stainless steel structure, wherein a stainless steel plate is attached to the surface of the stainless steel structure with the anticorrosion composition for a stainless steel substrate according to any one of claims 1 to 12.   The repaired stainless steel structure according to claim 17, wherein a surface of the stainless steel structure has a weld line formed when a stainless steel substrate is welded.   19. The repaired stainless steel structure according to claim 17, wherein the stainless steel structure is a water tank, a water tank, or a spent nuclear fuel storage pool.   A stainless steel structure characterized in that the surface of a stainless steel structure is coated with the anticorrosion composition for a stainless steel substrate according to any one of claims 1 to 12, and then a stainless steel plate is attached to the surface of the coating film. How to repair things.   The method for repairing a stainless steel structure according to claim 20, wherein a surface of the stainless steel structure has a weld line formed when a stainless steel base material is welded.   An anticorrosion method for a base material, comprising coating the surface of the stainless steel base material with an anticorrosive film formed from the anticorrosive composition for a stainless steel base material according to any one of claims 1 to 12. In the epoxy resin composition comprising (A) a main agent component and (B) a curing agent component,
The main agent component (A) contains a liquid epoxy resin (a1) and a silane coupling agent (a2), the curing agent component (B) contains an amine curing agent (b1),
The main component (A) and / or the curing agent component (B) contains a liquid hydrocarbon resin,
The amine curing agent is a Mannich-modified amine (b1-1) formed by an unsaturated substituent-containing phenol or a saturated substituent-containing phenol, formalin, and an amine compound, and / or an aliphatic polyamine. (B1-2),
The silane coupling agent (a2) is contained in an amount of 0.1 to 15% by weight in 100% by weight of the epoxy resin composition,
The liquid hydrocarbon resin is contained in the epoxy resin composition (100 wt%) in an amount of 1 to 50 wt%,
The Mannich-modified amine (b1-1) is contained in an amount of 10 to 40% by weight in 100% by weight of the curing agent component (B),
The aliphatic polyamine (b1-2) is contained in an amount of 10 to 40% by weight in 100% by weight of the curing agent component (B),
The epoxy equivalent of the liquid epoxy resin (a1) is in the range of 150 to 300,
The Mannich modified amine (b1-1) has an amine value (mgKOH / g) in the range of 300 to 500;
The active hydrogen equivalent (g / equiv) of the amino group of the aliphatic polyamine (b1-2) is 80 to 250,
The equivalent ratio represented by epoxy equivalent (g / equiv) in the main component (A) / active hydrogen equivalent (g / equiv) of amino group in the curing agent component (B) is 0.5-2. The component (A) and the component (B) are contained so as to be 0.0.
An adhesive composition for a stainless steel substrate, comprising an epoxy resin composition. The Mannich-modified amine (b1-1) is
A compound containing at least one monohydroxyphenyl group in the molecule and having 1 to 5 hydrogen atoms substituted with an unsaturated hydrocarbon group, phenol, divalent mononuclear phenol, divalent polynuclear phenol, alkylphenol (alkyl group) 1 to 10), halogenated phenol, alkoxyphenol (1 to 10 carbon atoms of alkoxy group), 2,2-di (p-hydroxyphenyl) -propane or di (p-hydroxyphenyl) -methane,
Formalin,
The adhesive composition for a stainless steel substrate according to claim 23, wherein the adhesive composition is a Mannich-modified amine formed by a Mannich condensation reaction with an amine compound.   25. The adhesive composition for a stainless steel substrate according to claim 23 or 24, wherein the aliphatic polyamine (b1-2) has an amine value (mgKOH / g) in the range of 300 to 500.   The adhesive composition for a stainless steel substrate according to any one of claims 23 to 25, wherein the main component (A) and / or the curing agent component (B) contains a color pigment and / or an extender pigment. object.   The equivalent ratio represented by epoxy equivalent (g / equiv) in the main component (A) / active hydrogen equivalent (g / equiv) of amino group in the curing agent component (B) is 0.8 to 1. 27. The stainless steel substrate adhesive composition according to any one of claims 23 to 26, wherein the (A) and the (B) are contained so as to be .5.   28. The epoxy resin composition comprising the silane coupling agent (a2) in an amount of 0.5 to 5% by weight in 100% by weight of the composition. The adhesive composition for stainless steel bases in any one.   The stainless steel according to any one of claims 23 to 28, wherein the colored pigment and / or the extender pigment is contained in an amount of 10 to 50% by volume in 100% by volume of the epoxy resin composition. An adhesive composition for a substrate.   30. The stainless steel according to claim 23, wherein the colored pigment and / or the extender pigment is contained in an amount of 15 to 30% by volume in 100% by volume of the epoxy resin composition. An adhesive composition for a substrate.   The color pigment and / or extender pigment is contained in an amount of 5 to 80 parts by weight with respect to 100 parts by weight of the curing agent component (B). Stainless steel substrate adhesive composition.   The liquid hydrocarbon resin is contained in an amount of 5 to 70% by weight in 100% by weight of the total amount of (a1), (a2), (b1) and the liquid hydrocarbon resin contained in the epoxy resin composition. 32. The adhesive composition for a stainless steel substrate according to any one of claims 23 to 31, wherein the adhesive composition is used.   The said main ingredient component (A) does not contain a solvent, The adhesive composition for stainless steel base materials in any one of Claims 23-32 characterized by the above-mentioned.   The adhesive composition for a stainless steel substrate according to any one of claims 23 to 33, wherein the adhesive composition is for underwater coating or wet surface coating.   A repaired stainless steel structure, wherein a stainless steel plate is attached to the surface of the stainless steel structure with the adhesive composition for a stainless steel substrate according to any one of claims 23 to 34.   36. The repaired stainless steel structure according to claim 35, wherein a surface of the stainless steel structure has a weld line formed when a stainless steel substrate is welded.   37. The repaired stainless steel structure according to claim 35 or 36, wherein the stainless steel structure is a water tank, a water tank, or a spent nuclear fuel storage pool.   A stainless steel structure characterized by applying the adhesive composition for a stainless steel substrate according to any one of claims 23 to 34 to the surface of a stainless steel structure, and then attaching a stainless steel plate to the surface of the coating film. How to repair structures.   The method for repairing a stainless steel structure according to claim 38, wherein a surface of the stainless steel structure has a weld line formed when a stainless steel base material is welded.

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