JP2004196945A - Curing epoxy resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curing epoxy resin composition which can form a cured product little in the generation of ammonia gas during curing, and good in initial hardness and beautiful in attire, etc., using an epoxy resin curing agent of low viscosity. <P>SOLUTION: This curing epoxy resin composition contains a Mannich compound (A) which is obtained by reacting a polyamine compound (a), a formaldehyde type compound (b), and a phenol compound (c), an amino compound (B) which is obtained by addition reaction of a diamine and an alkenyl compound and represented by general formula (I) and an epoxy compound (C). <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００１３】
【発明の実施の形態】
以下、本発明の硬化性エポキシ樹脂組成物について詳細に説明する。
【００１４】
本発明の硬化性エポキシ樹脂に使用される（Ａ）成分であるマンニッヒ化合物は、（ａ）ポリアミン化合物、（ｂ）ホルムアルデヒド類及び（ｃ）フェノール化合物を反応させて得られるものであり、硬化剤として用いられるものである。
【００１５】
上記マンニッヒ化合物（Ａ）の製造に使用される（ａ）成分であるポリアミン化合物としては、例えば、分子中に２個以上の１級又は２級アミノ基を有する化合物が挙げられ、該化合物としては、エチレンジアミン、ヘキサメチレンジアミン等のアルキレンジアミン；ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン等のポリアルキレンポリアミン；１，２−ジアミノシクロヘキサン、１，４−ジアミノ３，６−ジエチルシクロヘキサン、イソホロンジアミン等の脂環式ポリアミン；１，４−ビス（３−アミノプロピル）ピペラジン等の複素環式ポリアミン；ｍ−キシリレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン等の芳香族ポリアミン等が挙げられ、これらは単独でもあるいは混合併用してもよい。特にｍ−キシリレンジアミンは、硬化塗膜の硬化性、耐溶剤性及び防食性に優れるため望ましい。
【００１６】
また、上記マンニッヒ化合物（Ａ）の製造に使用される（ｂ）成分であるホルムアルデヒド類としては、ホルムアルデヒド；トリオキサン、パラホルムアルデヒド等のホルムアルデヒド放出性物質；ベンズアルデヒド等のアルデヒド類等が挙げられる。
【００１７】
また、上記マンニッヒ化合物（Ａ）の製造に使用される（ｃ）成分であるフェノール類としては、例えば、フェノール、クレゾール、ｐ−エチルフェノール、ｏ−イソプロピルフェノール、ｐ−イソプロピルフェノール、ｐ−ｔｅｒｔ−ブチルフェノール、ｐ−ｓｅｃ−ブチルフェノール、ｏ−ｔｅｒｔ−ブチルフェノール、ｏ−ｓｅｃ−ブチルフェノール、ｐ−ｔｅｒｔ−アミルフェノール、ｏ−ｔｅｒｔ−アミルフェノール、ｐ−オクチルフェノール、ノニルフェノール、ｐ−クミルフェノール、デシルフェノール、ウンデシルフェノール、ｐ−ドデシルフェノール、トリデシルフェノール、テトラデシルフェノール、ペンタデシルフェノール、ペンタデセニルフェノール、ペンタデカジエニルフェノール、ペンタデカトリエニルフェノール、ヘキサデシルフェノール、ヘプタデシルフェノール、オクタデシルフェノール、オクタデセニルフェノール、テルペンフェノール、更にはカルダノール等の天然に産出されるフェノール化合物及びこれらの混合物等が挙げられる。
【００１８】
これらの（ａ）、（ｂ）及び（ｃ）成分を反応させてマンニッヒ化合物（Ａ）を得る方法は、特に限定されるものではないが、例えば、（ａ）成分と（ｃ）成分との混合物に、（ｂ）成分を８０℃以下、好ましくは６０℃以下で滴下し、その後８０〜１８０℃、好ましくは９０〜１５０℃に昇温し、留出物を反応系から除去しながら１〜１０時間反応させることによって得る方法等が挙げられる。
【００１９】
ここで、（ｂ）成分は、（ａ）成分１モルに対し、好ましくは０．３〜２モル、更に好ましくは０．５〜１．５モルの範囲で使用される。（ａ）成分１モルに対する（ｂ）成分の使用量が０．３モル未満では付加が充分進行せず、低温硬化性、あるいは防食性等の物性低下を招くおそれがあり、２モルより多く使用した場合には重合度が大きくなり、粘度が高すぎて作業性が悪化したり、硬化の架橋密度が低くなりすぎるおそれがあるため好ましくない。
【００２０】
また、（ｃ）成分は、（ａ）成分１モルに対し、好ましくは０．３〜２モル、更に好ましくは０．５〜１．５モルの範囲で使用される。（ａ）成分１モルに対する（ｃ）成分の使用量が０．３モル未満では塗膜にアミンブラッシングや白化を生じる等、美装性が低下するおそれがあり、２モルを超えて使用した場合には活性点が不足するため硬化剤としての性能が充分発揮されないおそれがある。
【００２１】
本発明の硬化性エポキシ樹脂組成物に使用される（Ｂ）成分であるアミノ化合物は、ジアミンとアルケニル化合物との付加反応により得られるものであり、（Ａ）成分と組合わせて硬化剤として使用されるものである。（Ｂ）成分であるアミノ化合物は、特開２００２−１６１０７６号公報に記載されるような化合物に相当するものである。
【００２２】
上記アミノ化合物（Ｂ）の製造に使用されるジアミンは、アルケニル化合物と付加反応して、上記一般式（Ｉ）で表されるアミノ化合物を与え得るものであればよく、ｏ−キシリレンジアミン、ｍ−キシリレンジアミン、ｐ−キシリレンジアミン、１，２−ビス（アミノメチル）シクロヘキサン、１，３−ビス（アミノメチル）シクロヘキサン、１，４−ビス（アミノメチル）シクロヘキサン等が挙げられる。また、これらの混合物も使用することができる。
【００２３】
また、上記一般式（Ｉ）で表されるアミノ化合物を与え得るこれらのジアミンに、さらに他のジアミンを混合して使用することもできる。他のジアミンとしては、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、ヘキサメチレンジアミン、ポリオキシアルキレンポリアミン等の脂肪族ポリアミン；イソホロンジアミン、ノルボルナンジアミン、１，４−ジアミンシクロヘキサン、ジ（アミノヘキシル）メタン等の脂環族ポリアミン；メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン等の芳香族ポリアミン；Ｎ−アミノエチルピペラジン、３，９−ビス（３−アミノプロピル）２，４，８，１０−テトラオキサスピロ（５．５）ウンデカン等のヘテロ環族ポリアミン等が挙げられる。ただし、これらの他のジアミンの使用量は、全ジアミン中５０質量％を超えないものとする。
【００２４】
上記アミノ化合物（Ｂ）の製造に使用されるアルケニル化合物としては、エチレン、プロピレン、ブテン、ペンテン、ヘキセン、ヘプテン、オクテン、ノネン、デセン、イソブテン、２−ペンテン、３−メチル−１−ブテン、２−メチル−２−ブテン、２，３−ジメチル−２−ブテン、シクロヘキセン、シクロヘキサジエン、スチレン、α−メチルスチレン、ビニルベンゼン、ジビニルベンゼン等が挙げられる。これらの中でもスチレンが好ましい。
【００２５】
これらのジアミンとアルケニル化合物とを反応させてアミノ化合物（Ｂ）を得る方法は、特に限定されるものではないが、特開２００２−１６１０７６号公報に詳述されている製造方法等により得ることができ、例えば、不活性ガス下にてジアミンとアルケニル化合物との混合物を、リチウムアミド等の強塩基性触媒の存在下、常温〜１５０℃、好ましくは５０〜１００℃で反応させることで容易に得られる。
【００２６】
ここで、アルケニル化合物は、該アルケニル化合物中の炭素−炭素二重結合が、ジアミン１モルに対し、好ましくは０．１〜４モル、更に好ましくは０．５〜２モルとなる量で使用される。０．１モル未満の使用では、塗膜の美装性が低下しやすく、４モルを超えて使用した場合には、活性点が不足するため硬化剤としての性能が充分発揮されないおそれがある。
【００２７】
また、市販品のアミノ化合物（Ｂ）としては、例えば、ガスカミン２４０（三菱ガス化学（株）製）等が挙げられる。
【００２８】
本発明の硬化性エポキシ樹脂組成物に使用される（Ｃ）成分であるエポキシ化合物としては、例えば、ハイドロキン、レゾルシン、ピロカテコール、フロログルクシノール等の単核多価フェノール化合物のポリグリシジルエーテル化合物；ジヒドロキシナフタレン、ビフェノール、メチレンビスフェノール（ビスフェノールＦ）、メチレンビス（オルソクレゾール）、エチリデンビスフェノール、イソプロピリデンビスフェノール（ビスフェノールＡ）、イソプロピリデンビスビス（オルソクレゾール）、テトラブロムビスフェノールＡ、１，３−ビス（４−ヒドロキシクミルベンゼン）、１，４−ビス（４−ヒドロキシクミルベンゼン）、１，１，３−トリス（４−ヒドロキシフェニル）ブタン、１，１，２，２−テトラ（４−ヒドロキシフェニル）エタン、チオビスフェノール、スルホビスフェノール、オキシビスフェノール、フェノールノボラック、オルソクレゾールノボラック、レゾルシンノボラック等の多核多価フェノール化合物のポリグリシジルエーテル化合物；エチレングリコール、プロピレングリコール、ブチレングリコール、ヘキサンジオール、ポリグリコール、チオグリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、ビスフェノールＡ−エチレンオキサイド又はプロピレンオキサイド付加物等の多価アルコール類のポリグリシジルエーテル；マレイン酸、フマル酸、イタコン酸、コハク酸、グルタル酸、スベリン酸、アジピン酸、アゼライン酸、セバシン酸、ダイマー酸、トリマー酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、トリメシン酸、ピロメリット酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸等の脂肪族、芳香族又は脂環族多塩基酸のグリシジルエステル類及びグリシジルメタクリレートの単独重合体又は共重合体；Ｎ，Ｎ−ジグリシジルアニリン、ビス（４−（Ｎ−メチルーＮ−グリシジルアミノ）フェニル）メタン等のグリシジルアミノ基を有するエポキシ化合物；ビニルシクロヘキセンジエポキシド、ジシクロペンタジエンジエポキサイド、３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート、３，４−エポキシ−６−メチルシクロヘキシルメチル−３，４−エポキシ−６−メチルシクロヘキサンカルボキシレート、ビス（３，４−エポキシ−６−メチルシクロヘキシルメチル）アジペート等の環状オレフィン化合物のエポキシ化物；エポキシ化ポリブタジエン、エポキシ化スチレン−ブタジエン共重合物等のエポキシ化共役ジエン重合体、トリグリシジルイソシシアヌレート等の複素環化合物が挙げられる。
また、これらのエポキシ化合物は、ポリイソシアネート化合物若しくは末端イソシアネートのプレポリマーによって内部架橋されたものでも良い。
【００２９】
上記エポキシ化合物（Ｃ）は、エポキシ当量１００〜２０００、更に１５０〜１５００のものが好ましい。該エポキシ当量が１００未満では、硬化剤の配合部数が多くなりすぎ、仕上がり性、強度等が低下するおそれがあり、２０００よりも大きい場合には、充分な架橋密度が得られず、良好な塗膜物性が得られないおそれがある。
【００３０】
本発明の硬化性エポキシ樹脂組成物においては、上記エポキシ化合物（Ｃ）１００重量部に対し、上記マンニッヒ化合物（Ａ）及び上記アミノ化合物（Ｂ）を合計で好ましくは１〜６０重量部、更に好ましくは１０〜５０重量部配合する。（Ａ）成分及び（Ｂ）成分の合計量が１重量部未満の場合には、硬化が進行しないおそれがあり、６０重量部を超えた場合には、アミンブラッシングを生じるおそれがあるため好ましくない。
【００３１】
また、（Ａ）成分と（Ｂ）成分との重量比（Ａ）／（Ｂ）は、好ましくは１〜９９／９９〜１、更に好ましくは５〜９０／９０〜５、最も好ましくは１５〜８５／８５〜１５である。
【００３２】
本発明の硬化性エポキシ樹脂組成物は、必須成分である上記マンニッヒ化合物（Ａ）、上記アミノ化合物（Ｂ）及び上記エポキシ化合物（Ｃ）の他に、添加剤（Ｄ）を含有することができる。添加剤（Ｄ）としては、公知のエポキシ樹脂硬化剤、溶剤、反応性希釈剤、非反応性希釈剤、硬化触媒、充填剤、顔料、増粘剤、難燃剤、消泡剤、防錆剤、その他樹脂等が挙げられる。
【００３３】
上記の公知のエポキシ樹脂硬化剤としては、例えば、上記（ａ）成分として例示したポリアミン化合物、及びこれらのエポキシド付加変性物、アミド化変性物等が挙げられる。これらの公知のエポキシ樹脂硬化剤の使用量は、上記（Ａ）成分及び上記（Ｂ）成分の合計量１００重量部に対して、好ましくは１００重量部以下とする。
【００３４】
ここで、上記エポキシド付加変性物は、ポリアミン化合物とフェニルグリシジルエーテル、ブチルグリシジルエーテル、ビスフェノールＡ−ジグリシジルエーテル、ビスフェノールＦ−ジグリシジルエーテル等のグリシジルエーテル類又はカルボン酸のグリシジルエステル類等の各種エポキシ化合物とを常法によって反応させることによって製造される。
【００３５】
上記溶剤としては、例えば、テトラヒドロフラン、１，２−ジメトキシエタン、１，２−ジエトキシエタン等のエーテル類、イソ−又はｎ−ブタノール、イソ−又はｎ−プロパノール、アミルアルコール等のアルコール類、ベンゼン、トルエン、キシレン、ソルベッソ等の芳香族炭化水素、四塩化炭素、クロロホルム、トリクロロエチレン、塩化メチレン等のハロゲン化脂肪族炭化水素、クロロベンゼン等のハロゲン化芳香族炭化水素、アニリン、トリエチルアミン、ピリジン、ジオキサン、酢酸、アセトニトリル、二硫化炭素等が挙げられ、これらの溶剤は任意に２種以上の混合溶剤として用いることも可能である。一方、ケトン類及びエステル類は、硬化性を阻害するので好ましくない。
【００３６】
上記反応性希釈剤としては、例えば、モノグリシジルエーテル化合物、多官能グリシジルエーテル化合物が挙げられ、これらを使用することで、耐衝撃性、立ち上がり硬度等の物性面を改善することができる。該モノグリシジルエーテル化合物としては、例えば、フェノール、クレゾール、エチルフェノール、プロピルフェノール、ｐ−ｔｅｒｔ−ブチルフェノール、ｐ−ｔｅｒｔ−アミルフェノール、ヘキシルフェノール、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、オクタデシルフェノール、テルペンフェノール等のモノグリシジルエーテルが挙げられ、該多官能グリシジルエーテル化合物としては、例えば、１，６−ヘキサンジオール、メチルペンタンジオール、アジピン酸、グリセリン、トリメチロールプロパン等のグリシジルエーテルが挙げられ、これらは任意に２種以上の混合物として用いることも可能である。
【００３７】
上記非反応性希釈剤としては、例えば、ジオクチルフタレート、ジブチルフタレート、ベンジルアルコール、コールタール、キシレン樹脂、更には石油樹脂、テルペン樹脂等の粘着性の樹脂類が挙げられる。
【００３８】
上記硬化触媒としては、例えば、トリメチルアミン、エチルジメチルアミン、プロピルジメチルアミン、Ｎ，Ｎ’−ジメチルピペラジン、ピリジン、ピコリン、１，８−ジアザビスシクロ（５．４．０）ウンデセン−１（ＤＢＵ）、ベンジルジメチルアミン、２−（ジメチルアミノメチル）フェノール（ＤＭＰ−１０）、２，４，６−トリス（ジメチルアミノメチル）フェノール（ＤＭＰ−３０）等の第三アミン類、フェノールノボラック、ｏ−クレゾールノボラック、ｐ−クレゾールノボラック、ｔ−ブチルフェノールノボラック、ジシクロペンタジエンクレゾール等のフェノール類等が挙げられる。これらの硬化触媒の使用量は、上記（Ａ）成分、上記（Ｂ）成分及び必要に応じて使用される上記の公知のエポキシ樹脂硬化剤の総量１００重量部に対して、好ましくは２０重量部以下とする。
【００３９】
本発明の硬化性エポキシ樹脂組成物は、例えば、コンクリート、セメントモルタル、各種金属、皮革、ガラス、ゴム、プラスチック、木、布、紙等に対する塗料、接着剤、包装用粘着テープ、粘着ラベル、冷凍食品ラベル、リムーバルラベル、ＰＯＳラベル、粘着壁紙、粘着床材の粘着剤、アート紙、軽量コート紙、キャストコート紙、塗工板紙、カーボンレス複写機、含浸紙等の加工紙、天然繊維、合成繊維、ガラス繊維、炭素繊維、金属繊維等の収束剤、ほつれ防止剤、加工剤等の繊維処理剤、シーリング材、セメント混和剤、防水剤、塗り床材、防食塗料等の広範な用途に使用できる。
【００４０】
【実施例】
以下、製造例、実施例等を示して本発明の硬化性エポキシ樹脂組成物を更に詳述するが、本発明はこれらに限定されるものではない。
【００４１】
〔製造例１〕マンニッヒ化合物（Ｉ）の製造
加熱、冷却装置、攪拌装置、滴下装置、脱水装置を備えたフラスコにメタキシリレンジアミン１３６．０ｇ（１．０モル）及びフェノール９４ｇ（１．０モル）を仕込み、攪拌を開始し、系中温度を３０〜５０℃に調節しながら３７重量％ホルムアルデヒド水溶液８１ｇ（１．０モル）を６０〜１２０分かけて滴下した。滴下終了後、脱水装置を装着し、徐々に昇温し、１００〜１５０℃で５時間、反応で生成される水を留去しながら反応を進行させた。最後に１１０℃、８０ｍｍＨｇの減圧下において脱水反応を完結させ、最終生成物として褐色透明半固形で、アミン価４９０ｍｇＫＯＨ／ｇのマンニッヒ化合物（Ｉ）１８５ｇ（収率９７％）を得た。
【００４２】
〔製造例２〕マンニッヒ化合物（II）の製造
加熱、冷却装置、攪拌装置、滴下装置、脱水装置を備えたフラスコにメタキシリレンジアミン２７２．０ｇ（２．０モル）及びフェノール９４ｇ（１．０モル）を仕込み、攪拌を開始し、系中温度を３０〜５０℃に調節しながら３７重量％ホルムアルデヒド水溶液１６２ｇ（２．０モル）を１００〜２００分かけて滴下した。滴下終了後、脱水装置を装着し、徐々に昇温し、１００〜１５０℃で６時間、反応で生成される水を留去しながら反応を進行させた。最後に１１０℃、８０ｍｍＨｇの減圧下において脱水反応を完結させ、最終生成物として褐色透明半固形で、アミン価５２０ｍｇＫＯＨ／ｇのマンニッヒ化合物（II）２８０ｇ（収率９７％）を得た。
【００４３】
〔製造例３〕マンニッヒ化合物（III）の製造
加熱、冷却装置、攪拌装置、滴下装置、脱水装置を備えたフラスコにイソホロンジアミン１７０．０ｇ（１．０モル）及びフェノール９４ｇ（１．０モル）を仕込み、攪拌を開始し、系中温度を３０〜５０℃に調節しながら３７重量％ホルムアルデヒド水溶液８１ｇ（１．０モル）を６０〜１２０分かけて滴下した。滴下終了後、脱水装置を装着し、徐々に昇温し、１００〜１５０℃で５時間、反応で生成される水を留去しながら反応を進行させた。最後に１１０℃、８０ｍｍＨｇの減圧下において脱水反応を完結させ、最終生成物として褐色透明半固形で、アミン価４６０ｍｇＫＯＨ／ｇのマンニッヒ化合物（III）２２０ｇ（収率９８％）を得た。
【００４４】
〔製造例４〕マンニッヒ化合物（IV）の製造
加熱、冷却装置、攪拌装置、滴下装置、脱水装置を備えたフラスコにイソホロンジアミン３４０．０ｇ（２．０モル）及びフェノール９４ｇ（１．０モル）を仕込み、攪拌を開始し、系中温度を３０〜５０℃に調節しながら３７重量％ホルムアルデヒド水溶液１６２ｇ（２．０モル）を１００〜２００分かけて滴下した。滴下終了後、脱水装置を装着し、徐々に昇温し、１００〜１５０℃で６時間、反応で生成される水を留去しながら反応を進行させた。最後に１１０℃、８０ｍｍＨｇの減圧下において脱水反応を完結させ、最終生成物として褐色透明半固形で、アミン価５２０ｍｇＫＯＨ／ｇのマンニッヒ化合物（IV）４５０ｇ（収率９８％）を得た。
【００４５】
〔製造例５〕マンニッヒ化合物（Ｖ）の製造
加熱、冷却装置、攪拌装置、滴下装置、脱水装置を備えたフラスコにメタキシリレンジアミン１３６．０ｇ（１．０モル）及びｐ−ｔｅｒｔ−ブチルフェノール１５０ｇ（１．０モル）を仕込み、昇温しながら攪拌を開始し、７０〜１００℃程度で均一溶解させ、その後系中を冷却し、温度を３０〜５０℃に調節しながら３７重量％ホルムアルデヒド水溶液８１ｇ（１．０モル）を６０〜１２０分かけて滴下した。滴下終了後、脱水装置を装着し、徐々に昇温し、１００〜１５０℃で５時間、反応で生成される水を留去しながら反応を進行させた。最後に１１０℃、８０ｍｍＨｇの減圧下において脱水反応を完結させ、最終生成物として褐色透明半固形で、アミン価４２０ｍｇＫＯＨ／ｇのマンニッヒ化合物（Ｖ）２９０ｇ（収率９７％）を得た。
【００４６】
〔製造例６〜１１〕エポキシ樹脂硬化剤Ａ〜Ｆの調製
上記製造例１〜５において得られたマンニッヒ化合物（硬化剤ベース）に、ジアミンとスチレンとの付加反応により得られるアミノ化合物（商品名：ガスカミン２４０、三菱ガス化学社製）及び添加剤を〔表１〕に記載の割合で配合し、エポキシ樹脂硬化剤Ａ〜Ｆそれぞれを得た。得られたエポキシ樹脂硬化剤Ａ〜Ｆそれぞれの粘度及び活性水素当量を〔表１〕に示す。
【００４７】
【表１】

【００４８】
〔比較製造例１〜６〕エポキシ樹脂硬化剤ａ〜ｆの調製
上記製造例１〜５において得られたマンニッヒ化合物（硬化剤ベース）若しくは各種ポリアミン化合物に、添加剤を〔表２〕に記載の割合で配合し、エポキシ樹脂硬化剤ａ〜ｆそれぞれを得た。得られたエポキシ樹脂硬化剤ａ〜ｆそれぞれの粘度及び活性水素当量を〔表２〕に示す。
【００４９】
【表２】

【００５０】
〔実施例１〜６及び比較例１〜６〕
上記エポキシ樹脂硬化剤Ａ〜Ｆ及び上記エポキシ樹脂硬化剤ａ〜ｆのいずれかと、市販の液状低分子量エポキシ樹脂主剤（商品名：アデカレジンＥＰ−４１００、旭電化工業（株）製、エポキシ当量１９０、ビスフェノールＡ型ジグリシジルエーテル）とを、主剤／硬化剤＝１００／４０の重量比で配合し、硬化性エポキシ樹脂組成物（クリアワニス）を得た。
【００５１】
次いで、得られたクリアワニスを、コテを用いてスレート板上に厚さ１００μ程度に塗布し、１０℃又は２０℃雰囲気下で１６時間放置し、硬化塗膜を得た。得られた硬化塗膜それぞれについて、アミンブラッシング及び耐水白化それぞれを下記評価方法に従って評価し、且つ立ち上がり硬度（ShoreD）を下記測定方法に従って測定した。また、得られたクリアワニスの硬化時のアンモニアガス発生量を下記測定方法に従って測定した。これらの結果を〔表３〕及び〔表４〕に示す。
【００５２】
＜アミンブラッシング評価方法＞
塗膜表面を目視により観察し、以下の評価基準にて評価した。
（評価基準）
○：塗膜全面に全くアミン炭酸塩発生の曇りがなく異常なし。
△：塗膜表面一部にアミン炭酸塩発生の曇りあり。
×：塗膜全面にアミン炭酸塩発生の曇りが見受けられる。
【００５３】
＜耐水白化評価方法＞
塗膜表面上にスポイトで一滴水を垂らし、３０分後にふき取って、塗膜表面上の白化具合を観察し、以下の評価基準にて評価した。
（評価基準）
○：水滴をふき取った後にアミン炭酸塩析出の白化が全く見られない。
△：水滴をふき取った後にアミン炭酸塩析出の白化がやや薄いが見受けられる。
×：水滴をふき取った後にアミン炭酸塩析出の白化がかなり濃く見受けられる。
【００５４】
＜立ち上がり硬度測定方法＞
ＳｈｏｒｅＤ硬度計（業界標準品）により、硬化物の硬度を測定した。
【００５５】
＜アンモニアガス発生量測定方法＞
１００ｃｃの密閉ガラス容器中に、得られたクリアワニス７ｇ（主剤５ｇ／硬化剤２ｇ）をとり、２４時間放置して硬化させた。２４時間放置後の容器内のアンモニアガス量を、アンモニア検知管により測定した。
【００５６】
【表３】

【００５７】
【表４】

【００５８】
以上の実施例及び比較例から明らかなように、ポリアミン化合物、ホルムアルデヒド類及びフェノール化合物を反応させて得られるマンニッヒ化合物、及び互いに側鎖基の異なる付加化合物の混合物を含むものであるジアミンとスチレンとの付加反応により得られるアミノ化合物、並びにエポキシ化合物を含有する硬化性エポキシ樹脂組成物は、上記アミノ化合物を併用せず、マンニッヒ化合物、シアノエチル化ポリアミン、又はポリアミンをベースとし硬化触媒等の添加剤を配合した一般型硬化剤を用いたエポキシ樹脂組成物と比較して、粘度が低く、作業性が向上し、常温硬化におけるブラッシング、耐水白化等の仕上がり性に優れ、硬化物の立ち上がり硬度（ShoreD）も高いことが判る。また、硬化時に発生するアンモニアガスの量も、前者は後者に比べ１／３〜１／２程度に低減できることが判る。
【００５９】
【発明の効果】
本発明の硬化性エポキシ樹脂組成物は、ポリアミン化合物、ホルムアルデヒド類及びフェノール化合物を反応させて得られるマンニッヒ化合物と、ジアミンとアルケニル化合物との付加反応により得られるアミノ化合物を併用してなる配合物をエポキシ樹脂硬化剤として使用したものであり、低粘度で作業性が良好であり、且つ、優れた美装性及び高立ち上がり硬度を有し、硬化時のアンモニアガス発生量の少ない硬化物を提供するものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a curable epoxy resin composition, specifically, a polyamine compound, a Mannich compound obtained by reacting a formaldehyde and a phenol compound, and an amino compound obtained by an addition reaction of a diamine and an alkenyl compound in combination. A curable epoxy resin composition characterized by using a composition as an epoxy resin curing agent. The curable epoxy resin composition of the present invention has a long pot life, and can provide a cured product having good appearance, chemical resistance, corrosion resistance, and good adhesion to various substrates, Useful for paints, building materials, adhesives, etc.
[0002]
[Prior art]
Epoxy resins are widely used in paints, building materials, adhesives, and the like because of their low curing shrinkage, excellent adhesion to various substrates, heat resistance, chemical resistance, electrical properties, mechanical properties, and the like.
[0003]
When used for these applications, in many cases, a curing agent containing a Mannich compound is blended into an epoxy resin to be used as a curable epoxy resin composition. The Mannich compound is obtained by reacting an aliphatic or aromatic polyamine compound with formaldehydes and a phenol compound. By modifying the polyamine compound to have a high molecular weight in this manner, the raw material polyamine compound can be made less toxic and less irritating, and the potable life of the curable epoxy resin composition can be increased, Physical properties can be improved. Such a curing agent containing a Mannich compound is generally used particularly for applications such as paints and building materials used in the summer.
[0004]
However, since the Mannich compound has a high molecular weight, the viscosity of the curing agent itself increases considerably, and a large amount of a diluent, a solvent, and the like must be used in combination. It may not be suitable for applications such as paints and building materials. In addition, the combined use of a diluent, a solvent, and the like causes a decrease in the improved physical properties due to denaturation, and particularly in a building material application, a decrease in rising hardness, a decrease in strength, and the like, and a satisfactory cured product cannot be obtained. was there.
[0005]
In addition, in order to reduce the viscosity of the curing agent itself and improve the strength of the cured product, there is a method of blending the raw material polyamine compound itself such as polyalkylene polyamine, diluting the curing agent, and setting the obtained cured product. They tend to have poor finishes such as amine brushing properties and water whitening resistance and aesthetics, and are also not preferred in that they shorten the pot life.
[0006]
Furthermore, in both cases of the Mannich compound and the polyamine-diluted system, since a polyamine compound, particularly ammonia gas derived from meta-xylylenediamine is generated at the time of the curing reaction of the epoxy resin, environmental stimuli such as irritating odor, safety and health, etc. The current situation in the industry is that it is necessary to improve from the viewpoint of the problem, especially when it is used for paving construction of floors and interiors in a closed clean room.
[0007]
On the other hand, it has been proposed to use an amino compound obtained by an addition reaction between a diamine and an alkenyl compound as an epoxy resin curing agent (for example, see Patent Document 1). Epoxy resin curing agents using the amino compound are excellent in amine brushing properties, water whitening resistance, low viscosity, etc., but have extremely low rise hardness of cured products and poor mechanical properties such as tensile strength. It was not yet satisfactory.
[0008]
[Patent Document 1]
JP 2002-16076 A
[0009]
[Problems to be solved by the invention]
Therefore, an object of the present invention is to use a low-viscosity epoxy resin curing agent, to generate a small amount of ammonia gas at the time of curing, and to form a cured product having high rising hardness, good appearance and the like. An object of the present invention is to provide a curable epoxy resin composition.
[0010]
[Means for Solving the Problems]
The present inventors have conducted intensive studies and found that a compound comprising a combination of a Mannich compound obtained by reacting a polyamine compound, formaldehydes and a phenol compound, and an amino compound obtained by an addition reaction of a diamine and an alkenyl compound. Curable epoxy resin composition using the product as an epoxy resin curing agent has a long pot life, and good curing of aesthetics, chemical resistance, corrosion resistance, and adhesion to various substrates The present inventors have found that a product can be provided, and have reached the present invention.
[0011]
That is, the present invention relates to a Mannich compound (A) obtained by reacting (a) a polyamine compound, (b) a formaldehyde compound and (c) a phenol compound, and the following general formula (A) obtained by an addition reaction of a diamine and an alkenyl compound. A curable epoxy resin composition comprising the amino compound (B) represented by I) and the epoxy compound (C).
[0012]
Embedded image

[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the curable epoxy resin composition of the present invention will be described in detail.
[0014]
The Mannich compound as the component (A) used in the curable epoxy resin of the present invention is obtained by reacting (a) a polyamine compound, (b) a formaldehyde compound and (c) a phenol compound, and comprises a curing agent It is used as
[0015]
Examples of the polyamine compound as the component (a) used in the production of the Mannich compound (A) include a compound having two or more primary or secondary amino groups in the molecule. , Ethylenediamine, hexamethylenediamine and other alkylene diamines; diethylenetriamine, triethylenetetramine, tetraethylenepentamine and other polyalkylenepolyamines; 1,2-diaminocyclohexane, 1,4-diamino3,6-diethylcyclohexane, isophoronediamine and the like Alicyclic polyamines; heterocyclic polyamines such as 1,4-bis (3-aminopropyl) piperazine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone; Or mixed It may be use. Particularly, m-xylylenediamine is desirable because it has excellent curability, solvent resistance and corrosion resistance of the cured coating film.
[0016]
Examples of the formaldehyde as the component (b) used in the production of the Mannich compound (A) include formaldehyde; formaldehyde-releasing substances such as trioxane and paraformaldehyde; and aldehydes such as benzaldehyde.
[0017]
Examples of the phenol which is the component (c) used in the production of the Mannich compound (A) include phenol, cresol, p-ethylphenol, o-isopropylphenol, p-isopropylphenol, and p-tert-phenol. Butylphenol, p-sec-butylphenol, o-tert-butylphenol, o-sec-butylphenol, p-tert-amylphenol, o-tert-amylphenol, p-octylphenol, nonylphenol, p-cumylphenol, decylphenol, unbutylphenol Decylphenol, p-dodecylphenol, tridecylphenol, tetradecylphenol, pentadecylphenol, pentadecenylphenol, pentadecadienylphenol, pentadecatrienylpheno Le, hexadecyl phenol, heptadecyl phenol, octadecyl phenol, octadecenyl phenol, terpene phenol, more phenolic compounds and mixtures thereof which are naturally occurring, such as cardanol.
[0018]
The method of obtaining the Mannich compound (A) by reacting these components (a), (b) and (c) is not particularly limited. For example, the method of reacting the components (a) and (c) The component (b) is added dropwise to the mixture at a temperature of 80 ° C or lower, preferably 60 ° C or lower, and then the temperature is raised to 80 to 180 ° C, preferably 90 to 150 ° C. A method obtained by reacting for 10 hours is exemplified.
[0019]
Here, the component (b) is used in an amount of preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.5 mol, per 1 mol of the component (a). If the amount of the component (b) is less than 0.3 mol per 1 mol of the component (a), the addition does not proceed sufficiently, and there is a possibility that the physical properties such as low-temperature curability or anticorrosion properties may be reduced. In such a case, the degree of polymerization is increased, and the viscosity is too high, so that the workability may be deteriorated or the crosslink density of curing may be too low, which is not preferable.
[0020]
The component (c) is used in an amount of preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.5 mol, per 1 mol of the component (a). When the amount of the component (c) used is less than 0.3 mol per 1 mol of the component (a), the cosmetic properties may be deteriorated such as amine brushing or whitening of the coating film. Has insufficient active points and may not sufficiently exhibit the performance as a curing agent.
[0021]
The amino compound as the component (B) used in the curable epoxy resin composition of the present invention is obtained by an addition reaction between a diamine and an alkenyl compound, and is used as a curing agent in combination with the component (A). Is what is done. The amino compound as the component (B) corresponds to the compound described in JP-A-2002-161076.
[0022]
The diamine used in the production of the amino compound (B) may be any one which can give an amino compound represented by the general formula (I) by an addition reaction with an alkenyl compound, and may be o-xylylenediamine, Examples thereof include m-xylylenediamine, p-xylylenediamine, 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, and 1,4-bis (aminomethyl) cyclohexane. Also, mixtures thereof can be used.
[0023]
In addition, other diamines can be mixed with these diamines which can give the amino compound represented by the above general formula (I). Other diamines include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, and polyoxyalkylenepolyamine; and fats such as isophoronediamine, norbornanediamine, 1,4-diaminecyclohexane, and di (aminohexyl) methane. Aromatic polyamines; Aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone; N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5 .5) Heterocyclic polyamines such as undecane and the like. However, the amount of these other diamines shall not exceed 50% by mass of the total diamines.
[0024]
Examples of the alkenyl compound used for producing the amino compound (B) include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, isobutene, 2-pentene, 3-methyl-1-butene, and 2-methyl-1-butene. -Methyl-2-butene, 2,3-dimethyl-2-butene, cyclohexene, cyclohexadiene, styrene, α-methylstyrene, vinylbenzene, divinylbenzene and the like. Of these, styrene is preferred.
[0025]
The method for obtaining the amino compound (B) by reacting these diamines with the alkenyl compound is not particularly limited, but may be obtained by the production method described in JP-A-2002-161076, or the like. For example, it can be easily obtained by reacting a mixture of a diamine and an alkenyl compound under an inert gas in the presence of a strong basic catalyst such as lithium amide at room temperature to 150 ° C, preferably 50 to 100 ° C. Can be
[0026]
Here, the alkenyl compound is used in an amount such that the carbon-carbon double bond in the alkenyl compound is preferably 0.1 to 4 mol, more preferably 0.5 to 2 mol, per 1 mol of the diamine. You. When the amount is less than 0.1 mol, the aesthetics of the coating film is apt to be deteriorated, and when the amount exceeds 4 mol, there is a possibility that the performance as a curing agent may not be sufficiently exhibited due to insufficient active sites.
[0027]
Examples of commercially available amino compounds (B) include, for example, Gascamine 240 (manufactured by Mitsubishi Gas Chemical Co., Ltd.).
[0028]
Examples of the epoxy compound which is the component (C) used in the curable epoxy resin composition of the present invention include polyglycidyl ethers of mononuclear polyhydric phenol compounds such as hydroquine, resorcinol, pyrocatechol and phloroglucinol. Compounds: dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebisbis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4- Hydroxy Enyl) polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, resorcinol novolak; ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, Polyglycidyl ethers of polyhydric alcohols such as thioglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide or propylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, Suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, tele Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids and glycidyl methacrylates such as tallic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endmethylenetetrahydrophthalic acid, etc. Homopolymer or copolymer; Epoxy compound having glycidylamino group such as N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane; vinylcyclohexene diepoxide, dicyclopentadiene Diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, bis (3,4 −Epo Epoxy products of cyclic olefin compounds such as (xy-6-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene, epoxidized styrene-butadiene copolymer, and heterocyclic compounds such as triglycidyl isocyanurate Is mentioned.
Further, these epoxy compounds may be those internally crosslinked by a polyisocyanate compound or a prepolymer of terminal isocyanate.
[0029]
The epoxy compound (C) preferably has an epoxy equivalent of 100 to 2000, more preferably 150 to 1500. If the epoxy equivalent is less than 100, the number of curing agents is too large, and finishability and strength may be reduced. If it is more than 2,000, sufficient cross-linking density cannot be obtained, resulting in good coating. Film properties may not be obtained.
[0030]
In the curable epoxy resin composition of the present invention, the total amount of the Mannich compound (A) and the amino compound (B) is preferably 1 to 60 parts by weight, more preferably 100 parts by weight of the epoxy compound (C). Is blended in an amount of 10 to 50 parts by weight. If the total amount of the components (A) and (B) is less than 1 part by weight, curing may not proceed, and if it exceeds 60 parts by weight, amine brushing may occur, which is not preferable. .
[0031]
The weight ratio (A) / (B) of the component (A) to the component (B) is preferably 1 to 99/99 to 1, more preferably 5 to 90/90 to 5, and most preferably 15 to 90. 85 / 85-15.
[0032]
The curable epoxy resin composition of the present invention can contain an additive (D) in addition to the Mannich compound (A), the amino compound (B) and the epoxy compound (C), which are essential components. . As the additives (D), known epoxy resin curing agents, solvents, reactive diluents, non-reactive diluents, curing catalysts, fillers, pigments, thickeners, flame retardants, defoamers, rust inhibitors And other resins.
[0033]
Examples of the known epoxy resin curing agent include the polyamine compounds exemplified as the component (a), and epoxide addition modified products and amidation modified products thereof. The amount of use of these known epoxy resin curing agents is preferably 100 parts by weight or less based on 100 parts by weight of the total of the above components (A) and (B).
[0034]
Here, the epoxide addition-modified product is a polyamine compound and various epoxy compounds such as glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether or glycidyl esters of carboxylic acid. It is produced by reacting a compound with a conventional method.
[0035]
Examples of the solvent include ethers such as tetrahydrofuran, 1,2-dimethoxyethane and 1,2-diethoxyethane, alcohols such as iso- or n-butanol, iso- or n-propanol, and amyl alcohol, and benzene. , Toluene, xylene, aromatic hydrocarbons such as Solvesso, carbon tetrachloride, chloroform, trichloroethylene, halogenated aliphatic hydrocarbons such as methylene chloride, halogenated aromatic hydrocarbons such as chlorobenzene, aniline, triethylamine, pyridine, dioxane, Acetic acid, acetonitrile, carbon disulfide and the like can be mentioned, and these solvents can be optionally used as a mixed solvent of two or more kinds. On the other hand, ketones and esters are not preferred because they inhibit curability.
[0036]
Examples of the reactive diluent include a monoglycidyl ether compound and a polyfunctional glycidyl ether compound. By using these compounds, physical properties such as impact resistance and rising hardness can be improved. Examples of the monoglycidyl ether compound include phenol, cresol, ethylphenol, propylphenol, p-tert-butylphenol, p-tert-amylphenol, hexylphenol, octylphenol, nonylphenol, dodecylphenol, octadecylphenol, terpenephenol and the like. Monoglycidyl ethers are exemplified. Examples of the polyfunctional glycidyl ether compounds include glycidyl ethers such as 1,6-hexanediol, methylpentanediol, adipic acid, glycerin, and trimethylolpropane. It is also possible to use as a mixture of more than one species.
[0037]
Examples of the non-reactive diluent include tacky resins such as dioctyl phthalate, dibutyl phthalate, benzyl alcohol, coal tar, xylene resin, and petroleum resin and terpene resin.
[0038]
Examples of the curing catalyst include trimethylamine, ethyldimethylamine, propyldimethylamine, N, N'-dimethylpiperazine, pyridine, picoline, 1,8-diazabiscyclo (5.4.0) undecene-1 (DBU), benzyl Tertiary amines such as dimethylamine, 2- (dimethylaminomethyl) phenol (DMP-10), 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30), phenol novolak, o-cresol novolak, Examples include phenols such as p-cresol novolak, t-butylphenol novolak, and dicyclopentadiene cresol. The amount of these curing catalysts used is preferably 20 parts by weight based on 100 parts by weight of the total of the above-mentioned component (A), the above-mentioned component (B), and the above-mentioned known epoxy resin curing agent used as required. The following is assumed.
[0039]
The curable epoxy resin composition of the present invention includes, for example, paints, adhesives, adhesive tapes for packaging, adhesive labels, adhesive labels on concrete, cement mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc. Food labels, removable labels, POS labels, adhesive wallpaper, adhesive flooring adhesive, art paper, lightweight coated paper, cast coated paper, coated paperboard, carbonless copier, impregnated paper and other processed paper, natural fibers, synthetic Used in a wide range of applications such as sizing agents such as fibers, glass fibers, carbon fibers, and metal fibers, anti-fray agents, fiber treatment agents such as processing agents, sealing materials, cement admixtures, waterproofing agents, floor coatings, and anticorrosive paints. it can.
[0040]
【Example】
Hereinafter, the curable epoxy resin composition of the present invention will be described in more detail with reference to Production Examples and Examples, but the present invention is not limited thereto.
[0041]
[Production Example 1] Production of Mannich compound (I)
136.0 g (1.0 mol) of metaxylylenediamine and 94 g (1.0 mol) of phenol were charged into a flask equipped with a heating / cooling device, a stirring device, a dropping device, and a dehydrating device, and stirring was started. While adjusting the temperature to 30 to 50 ° C., 81 g (1.0 mol) of a 37% by weight aqueous formaldehyde solution was added dropwise over 60 to 120 minutes. After completion of the dropwise addition, a dehydrator was attached, the temperature was gradually raised, and the reaction was allowed to proceed at 100 to 150 ° C. for 5 hours while distilling off water generated by the reaction. Finally, the dehydration reaction was completed at 110 ° C. under a reduced pressure of 80 mmHg to obtain 185 g (97% yield) of a Mannich compound (I) having an amine value of 490 mgKOH / g as a brown transparent semisolid as a final product.
[0042]
[Production Example 2] Production of Mannich compound (II)
272.0 g (2.0 mol) of metaxylylenediamine and 94 g (1.0 mol) of phenol were charged into a flask equipped with a heating / cooling device, a stirring device, a dropping device, and a dehydrating device, and stirring was started. While adjusting the temperature to 30 to 50 ° C., 162 g (2.0 mol) of a 37% by weight aqueous formaldehyde solution was added dropwise over 100 to 200 minutes. After completion of the dropping, a dehydrator was attached, the temperature was gradually raised, and the reaction was allowed to proceed at 100 to 150 ° C. for 6 hours while distilling off water generated by the reaction. Finally, the dehydration reaction was completed at 110 ° C. under a reduced pressure of 80 mmHg to obtain 280 g (97% yield) of a Mannich compound (II) having a amine value of 520 mgKOH / g as a brown transparent semisolid as a final product.
[0043]
[Production Example 3] Production of Mannich compound (III)
170.0 g (1.0 mol) of isophoronediamine and 94 g (1.0 mol) of phenol were charged into a flask equipped with a heating / cooling device, a stirring device, a dropping device, and a dehydrating device, and stirring was started. While controlling the temperature at 30 to 50 ° C., 81 g (1.0 mol) of a 37% by weight aqueous formaldehyde solution was added dropwise over 60 to 120 minutes. After completion of the dropwise addition, a dehydrator was attached, the temperature was gradually raised, and the reaction was allowed to proceed at 100 to 150 ° C. for 5 hours while distilling off water generated by the reaction. Finally, the dehydration reaction was completed at 110 ° C. under a reduced pressure of 80 mmHg to obtain 220 g (98% yield) of a Mannich compound (III) having an amine value of 460 mgKOH / g as a brown transparent semi-solid as a final product.
[0044]
[Production Example 4] Production of Mannich compound (IV)
340.0 g (2.0 mol) of isophoronediamine and 94 g (1.0 mol) of phenol were charged into a flask equipped with a heating / cooling device, a stirring device, a dropping device, and a dehydrating device, and stirring was started. While adjusting the temperature to 30 to 50 ° C., 162 g (2.0 mol) of a 37% by weight aqueous solution of formaldehyde was added dropwise over 100 to 200 minutes. After completion of the dropping, a dehydrator was attached, the temperature was gradually raised, and the reaction was allowed to proceed at 100 to 150 ° C. for 6 hours while distilling off water generated by the reaction. Finally, the dehydration reaction was completed at 110 ° C. under a reduced pressure of 80 mmHg to obtain 450 g (yield 98%) of a Mannich compound (IV) having an amine value of 520 mgKOH / g as a brown transparent semisolid as a final product.
[0045]
[Production Example 5] Production of Mannich compound (V)
136.0 g (1.0 mol) of meta-xylylenediamine and 150 g (1.0 mol) of p-tert-butylphenol were charged into a flask equipped with a heating / cooling device, a stirring device, a dropping device, and a dehydrating device, and heated. While stirring, the mixture was uniformly dissolved at about 70 to 100 ° C., then the system was cooled, and while adjusting the temperature to 30 to 50 ° C., 81 g (1.0 mol) of a 37% by weight aqueous formaldehyde solution was added for 60 to 120 minutes. The solution was dropped. After completion of the dropwise addition, a dehydrator was attached, the temperature was gradually raised, and the reaction was allowed to proceed at 100 to 150 ° C. for 5 hours while distilling off water generated by the reaction. Finally, the dehydration reaction was completed at 110 ° C. under a reduced pressure of 80 mmHg to obtain 290 g (97% yield) of a Mannich compound (V) having an amine value of 420 mgKOH / g as a brown transparent semisolid as a final product.
[0046]
[Production Examples 6 to 11] Preparation of epoxy resin curing agents A to F
An amino compound (trade name: Gascamine 240, manufactured by Mitsubishi Gas Chemical Company) and an additive obtained by an addition reaction of diamine and styrene were added to the Mannich compound (hardening agent base) obtained in Production Examples 1 to 5 above [Table 1] to obtain epoxy resin curing agents A to F, respectively. The viscosity and active hydrogen equivalent of each of the obtained epoxy resin curing agents A to F are shown in [Table 1].
[0047]
[Table 1]

[0048]
[Comparative Production Examples 1 to 6] Preparation of epoxy resin curing agents a to f
Additives were added to the Mannich compound (hardening agent base) or various polyamine compounds obtained in Production Examples 1 to 5 at the ratios shown in Table 2 to obtain epoxy resin curing agents a to f, respectively. The viscosity and active hydrogen equivalent of each of the obtained epoxy resin curing agents a to f are shown in [Table 2].
[0049]
[Table 2]

[0050]
[Examples 1 to 6 and Comparative Examples 1 to 6]
Any one of the epoxy resin curing agents A to F and the epoxy resin curing agents a to f, and a commercially available liquid low molecular weight epoxy resin main agent (trade name: ADEKARESIN EP-4100, manufactured by Asahi Denka Kogyo KK, epoxy equivalent 190, Bisphenol A type diglycidyl ether) was blended in a weight ratio of main agent / curing agent = 100/40 to obtain a curable epoxy resin composition (clear varnish).
[0051]
Next, the obtained clear varnish was applied to a thickness of about 100 μ on a slate plate using a trowel, and allowed to stand in a 10 ° C or 20 ° C atmosphere for 16 hours to obtain a cured coating film. For each of the obtained cured coating films, amine brushing and water whitening resistance were evaluated according to the following evaluation methods, and rise hardness (ShoreD) was measured according to the following measurement methods. Further, the amount of ammonia gas generated during curing of the obtained clear varnish was measured according to the following measuring method. The results are shown in [Table 3] and [Table 4].
[0052]
<Amine brushing evaluation method>
The coating film surface was visually observed and evaluated according to the following evaluation criteria.
(Evaluation criteria)
：: There was no clouding of amine carbonate generation on the entire surface of the coating film, and no abnormality was found.
Δ: Some surface of the coating film was clouded by amine carbonate generation.
X: Clouding of amine carbonate generation is observed on the entire surface of the coating film.
[0053]
<Water whitening evaluation method>
One drop of water was dropped on the surface of the coating film with a dropper, wiped out after 30 minutes, observed for the degree of whitening on the surface of the coating film, and evaluated according to the following evaluation criteria.
(Evaluation criteria)
：: No whitening of amine carbonate precipitation was observed after wiping off water droplets.
Δ: Whitening of amine carbonate precipitation is slightly observed after wiping off water droplets.
X: The whitening of amine carbonate precipitation is found to be quite deep after wiping off water droplets.
[0054]
<Rising hardness measurement method>
The hardness of the cured product was measured using a Shore D hardness meter (industry standard product).
[0055]
<Ammonia gas generation amount measurement method>
In a 100 cc closed glass container, 7 g of the obtained clear varnish (5 g of the main agent / 2 g of the curing agent) was taken and left to cure for 24 hours. After standing for 24 hours, the amount of ammonia gas in the container was measured with an ammonia detector tube.
[0056]
[Table 3]

[0057]
[Table 4]

[0058]
As is clear from the above Examples and Comparative Examples, polyamine compounds, Mannich compounds obtained by reacting formaldehydes and phenol compounds, and addition of diamine and styrene containing a mixture of addition compounds having different side chain groups from each other. The amino compound obtained by the reaction, and the curable epoxy resin composition containing the epoxy compound were not used in combination with the amino compound, and were mixed with an additive such as a curing catalyst based on a Mannich compound, a cyanoethylated polyamine, or a polyamine. Compared with the epoxy resin composition using a general type curing agent, the viscosity is low, the workability is improved, the finish such as brushing and water whitening at room temperature curing is excellent, and the rise hardness (ShoreD) of the cured product is high. You can see that. Also, it can be seen that the amount of ammonia gas generated at the time of curing can be reduced to about は to 前 in the former as compared to the latter.
[0059]
【The invention's effect】
The curable epoxy resin composition of the present invention is a polyamine compound, a Mannich compound obtained by reacting a formaldehyde and a phenol compound, and a compound obtained by using an amino compound obtained by an addition reaction of a diamine and an alkenyl compound in combination. Used as an epoxy resin curing agent, to provide a cured product having low viscosity, good workability, and excellent appearance and high rising hardness, and having a small amount of ammonia gas generated during curing. Things.

Claims (5)

(A) a Mannich compound (A) obtained by reacting a polyamine compound, (b) formaldehydes and (c) a phenol compound, and represented by the following general formula (I) obtained by an addition reaction of a diamine and an alkenyl compound. A curable epoxy resin composition comprising an amino compound (B) and an epoxy compound (C).

The Mannich compound (A) is obtained by reacting (b) 0.3 to 2 mol of formaldehyde and (c) 0.3 to 2 mol of a phenol compound with respect to 1 mol of the polyamine compound (a). The curable epoxy resin composition according to claim 1, wherein The curable epoxy resin composition according to claim 1, wherein the amino compound (B) is obtained by using styrene as an alkenyl compound. The weight ratio between the Mannich compound (A) and the amino compound (B) is (A) / (B) = 1 to 99/99 to 1, wherein the weight ratio is 1 to 99/99 to 1. The curable epoxy resin composition according to the above. The weight ratio of the Mannich compound (A) and the amino compound (B) is (A) / (B) = 5-90 / 90-5 and 100 parts by weight of the epoxy compound (C). The curable epoxy resin composition according to any one of claims 1 to 4, further comprising 1 to 60 parts by weight of a total amount of (C) and an additive (D) such as a curing catalyst.