JP4310614B2 - Polyamino epoxy resin curing agent and epoxy resin composition - Google Patents
Polyamino epoxy resin curing agent and epoxy resin composition Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、変性ポリアミノ化合物と特定構造のポリアミノ化合物を主成分とするポリアミノ組成物を特定範囲で混合した混合物からなるポリアミノ系エポキシ樹脂硬化剤、該エポキシ樹脂硬化剤を含むエポキシ樹脂組成物、該エポキシ樹脂組成物を硬化させたエポキシ樹脂硬化物に関する。
【０００２】
【従来の技術】
各種ポリアミノ化合物がエポキシ樹脂硬化剤およびその原料として広く用いられていることは良く知られている。これらポリアミノ化合物はそのままエポキシ樹脂硬化剤として用いられることは少なく、通常は安全衛生面の改善、作業性の改善、硬化物性能の改善などの目的に応じて、それぞれのアミノ基の反応性、すなわち活性水素に起因する特徴に適した変性を行ってから用いられることが殆どである。これらのエポキシ樹脂硬化剤を利用したエポキシ樹脂組成物は、特に船舶・橋梁・陸海上鉄構築物用防食塗料などの塗料分野、コンクリート構造物のライニング・補強・補修、建築物の床材、上下水道設備のライニング、舗装材、接着材などの土木・建築分野に広く利用されている。
【０００３】
代表的なポリアミノ化合物としては、脂肪族ポリアミノ化合物、例えばエチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサメチレンジアミンなど、芳香環を持った脂肪族ポリアミノ化合物、例えばキシリレンジアミンなど、脂環族ポリアミノ化合物、例えばメンセンジアミン、イソホロンジアミン、ビス（アミノメチル）シクロヘキサン、Ｎ−アミノメチルピペラジンなど、芳香族ポリアミノ化合物、例えば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フォンなど、その他ポリエーテル骨格のポリアミノ化合物、ノルボルナン骨格のポリアミノ化合物などがあげられる。
【０００４】
ポリアミノ化合物の代表的な変性方法としては、（１）フェノール系化合物とアルデヒド化合物とのマンニッヒ反応による変性、（２）エポキシ化合物との反応による変性、（３）カルボキシル基を有する化合物との反応による変性、（４）アクリル系化合物とのマイケル付加反応による変性、および（５）これらの組み合わせによる変性などがあげられる。
【０００５】
ポリアミノ化合物の変性比率（変性度合）は、一般的には、得られる変性ポリアミノ化合物がポリアミノ化合物由来の活性水素を持つアミノ基を有する範囲で選ばれる。しかしながら、変性比率が低い場合には変性ポリアミノ化合物の粘度は低くなるが、未反応（未変性）ポリアミノ化合物含有量が高くなるために、エポキシ樹脂硬化剤として利用した場合に、十分なエポキシ樹脂硬化物性能が得られない場合がある。一方、変性比率が高い場合には未反応ポリアミノ化合物含有量は低くなるが、粘度が高くなるために、作業性の改善を目的に溶剤や希釈剤を添加して低粘度化が必要となる。溶剤の添加は環境問題から避けることが望まれ、希釈剤の添加はエポキシ樹脂硬化物性能の低下を生ずるために添加量を制限する必要がある。
【０００６】
【発明が解決しようとする課題】
本発明の目的は、低粘度で、未反応ポリアミノ化合物含有量が低く、良好なエポキシ樹脂硬化物性能を与えるポリアミノ系エポキシ樹脂硬化剤、該エポキシ樹脂硬化剤を含むエポキシ樹脂組成物、該エポキシ樹脂組成物を硬化させたエポキシ樹脂硬化物を提供することである。
【０００７】
【課題を解決するための手段】
本発明者らは、鋭意検討した結果、変性ポリアミノ化合物と特定構造のポリアミノ化合物を主成分とするポリアミノ組成物の混合物からなるポリアミノ系エポキシ樹脂硬化剤は、変性ポリアミノ化合物をエポキシ樹脂硬化剤と使用した場合と比較して、低粘度で、未反応ポリアミノ化合物含有量が低いこと、また、該ポリアミノ系エポキシ樹脂硬化剤を含むエポキシ樹脂組成物は、変性ポリアミノ化合物をエポキシ樹脂硬化剤として含むエポキシ樹脂組成物を硬化させたエポキシ樹脂硬化物の性能を損なうことなく、良好なエポキシ樹脂硬化物を与えることを見出して本発明に至った。
【０００８】
即ち本発明は、分子内に少なくとも２個以上のアミノ基を有し、且つ該アミノ基に由来する活性水素を有するポリアミノ化合物Ａを原料とする変性ポリアミノ化合物と、（１）式で示されるポリアミノ化合物Ｂとスチレンとの付加反応により得られ、（２）式で示される互いに側鎖基の構成が異なる各付加物から選ばれる少なくとも１つであるポリアミノ化合物Ｃを主成分とするポリアミノ組成物の混合物からなるポリアミノ系エポキシ樹脂硬化剤を提供する。
さらに本発明は、該エポキシ樹脂硬化剤を含むエポキシ樹脂組成物、該エポキシ樹脂組成物を硬化させたエポキシ樹脂硬化物を提供する。
【化３】
【発明の実施の形態】
本発明で使用されるポリアミノ化合物Ａは、分子内に少なくとも２個以上のアミノ基を有し、且つ該アミノ基に由来する活性水素を有する化合物であり、具体的には、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、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサメチレンジアミン等の脂肪族ポリアミノ化合物、キシリレンジアミン等の芳香環を持った脂肪族ポリアミノ化合物、メンセンジアミン、イソホロンジアミン、ビス（アミノメチル）シクロヘキサン、Ｎ−アミノメチルピペラジン等の脂環族ポリアミノ化合物、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フォン等の芳香族ポリアミノ化合物、ポリエーテル骨格のポリアミノ化合物、ノルボルナン骨格のポリアミノ化合物等があげられる。これらは単独あるいは混合物として用いられる。
【００１０】
本発明の変性ポリアミノ化合物は、前記ポリアミノ化合物Ａを、以下の各変性方法、即ち、（１）フェノール系化合物とアルデヒド化合物とのマンニッヒ反応による変性、（２）エポキシ化合物との反応による変性、（３）カルボキシル基を有する化合物との反応による変性、（４）アクリル系化合物とのマイケル付加反応による変性、および（５）これらの組み合わせによる変性などにより変性することで合成される。
【００１１】
本発明のポリアミノ化合物Ａの変性比率は、得られる変性ポリアミノ化合物が活性水素を持つアミノ基を含有する様な比率であれば特に限定はされない。
【００１２】
本発明で使用される（１）式で示されるポリアミノ化合物Ｂとしては、オルソキシリレンジアミン、メタキシリレンジアミン、パラ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）シクロヘキサンなどがあげられる。これらの中で特に好ましいのは、メタキシリレンジアミン、１，３−ビス（アミノメチル）シクロヘキサンである。
【００１３】
本発明で使用されるポリアミノ化合物Ｃとは、前記ポリアミノ化合物Ｂとスチレンとの付加反応により得られ、（２）式で示される互いに側鎖基の構成が異なる各付加物から選ばれる少なくとも１つの化合物である。ここで、互いに側鎖基の構成が異なる各化合物とは、（２）式において、Ｒ１、Ｒ２およびＲ３のいずれもが水素である付加物、いずれか２つが水素であり、残り１つがフェネチル基である付加物、いずれか２つがフェネチル基であり、残り１つが水素である付加物、およびいずれもがフェネチル基である付加物である。
本発明では、これらの付加物は単独あるいは混合物として用いられる。
【００１４】
本発明において、ポリアミノ化合物Ｃを合成する際には、強塩基性を呈する触媒を使用することが好ましい。例えば、アルカリ金属、アルカリ金属アミド、アルキル化アルカリ金属などがあるが、好ましくはアルカリ金属アミド（一般式ＭＮＲＲ’：Ｍはアルカリ金属、Ｎは窒素、ＲおよびＲ’は各々独立して水素またはアルキル基である）であり、特にリチウムアミド（ＬｉＮＨ2）が好ましい。
【００１５】
本発明のエポキシ樹脂硬化剤は、前記変性ポリアミノ化合物と、ポリアミノ化合物Ｃを主成分とするポリアミノ組成物の混合物である。変性ポリアミノ化合物とポリアミノ組成物の混合重量比は、２：８〜８：２の範囲、特に好ましくは４：６〜６：４の範囲で選ばれる。変性ポリアミノ化合物の混合重量比が２より低い場合には、変性ポリアミノ化合物をエポキシ樹脂硬化剤として使用した場合のエポキシ樹脂硬化物性能が損なわれる場合があり、８より高い場合には、ポリアミノ系硬化剤は低粘度化が十分でなく、また、未反応ポリアミノ化合物含有量低減化も十分ではないため、好ましくない。
【００１６】
本発明のエポキシ樹脂組成物は、前記エポキシ樹脂硬化剤とエポキシ樹脂とからなる。該組成物に使用されるエポキシ樹脂はビスフェノールＡ型エポキシ樹脂またはビスフェノールＦ型エポキシ樹脂が、それぞれ単独で、あるいは混合して用いられるが、本発明のエポキシ樹脂硬化剤の活性水素と反応するグリシジル基を持つエポキシ樹脂であればいずれも使用することができ、これに限定されるものではない。さらに本発明のエポキシ樹脂組成物には、充填材、可塑剤などの改質成分、希釈剤、揺変剤などの流動調整成分、顔料、レベリング剤、粘着付与剤などのその他の成分を用途に応じて添加して用いることができる。本発明のエポキシ樹脂組成物を硬化させることにより、硬化塗膜等の各種硬化物が得られる。
【００１７】
【実施例】
以下に、本発明を実施例により具体的に説明するが、本発明はこれらの実施例により限定されるものではない。
【００１８】
〈変性ポリアミノ化合物の合成〉
合成例１
撹拌装置、温度計、窒素導入管、滴下漏斗、冷却管を備えた２リットルフラスコに、メタキシリレンジアミン（三菱ガス化学(株)製、以下ＭＸＤＡと記す）６１２.９g（４.５モル）とフェノール（和光純薬(株)製、試薬一級）４２３.４５g（４.５モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、ホルマリン（三菱ガス化学(株)製、８%メタノール含有３７%水溶液）２４３.３g（３.０モル）を１.５時間かけて滴下した。滴下終了後、１００℃に昇温し、１.５時間反応を行った。その後生成水を留去しながら２時間かけて１５０℃まで昇温し、同温度で１時間反応を行い、マンニッヒ反応による変性ポリアミノ化合物Ａ１０６８.２gを得た。変性ポリアミノ化合物Ａの粘度は２４５０mPa・s/25℃、未反応ＭＸＤＡ量は３０.０wt%であった。
【００１９】
合成例２
合成例１と同様のフラスコにＭＸＤＡ８１７.２ｇ（６.０モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、ビスフェノールＡジグリシジルエーテル（ジャパンエポキシレジン(株)製、商品名：エピコート８２８、エポキシ当量：１９０g/eq）４５６.０gを２時間かけて滴下した。滴下終了後、１００℃に昇温して２時間反応を行い、変性ポリアミノ化合物Ｂ１２６４.８gを得た。変性ポリアミノ化合物Ｂの粘度は９８４０mPa・s/25℃、未反応ＭＸＤＡ量は４８.４wt%であった。
【００２０】
合成例３
合成例１において、ＭＸＤＡを１,３-ビス（アミノメチル）シクロヘキサン（三菱ガス化学(株)製、以下１,３-ＢＡＣと記す）６３９.９ｇ（４.５モル）に代えた以外は同様の条件で合成を行い、変性ポリアミノ化合物Ｃ１０９１.８gを得た。変性ポリアミノ化合物Ｃの粘度は４３６０mPa・ｓ/25℃、未反応１,３-ＢＡＣ量は３１.２wt%であった。
【００２１】
合成例４
合成例２において、ＭＸＤＡを１,３-ＢＡＣ８５３.２g（６.０モル）に代えた以外は同様の条件で合成を行い、変性ポリアミノ化合物Ｄ１２９８.４gを得た。変性ポリアミノ化合物Ｄの粘度は１２５００mPa・s/25℃、未反応１,３-ＢＡＣ量は５０.３wt%であった。
【００２２】
〈ポリアミノ組成物の合成〉
合成例５
撹拌装置、温度計、窒素導入管、滴下漏斗、冷却管を備えた２リットルフラスコに、ＭＸＤＡ８１７.２g（６.０モル）とリチウムアミド（Ｍｅｒｋ社製、試薬）２.９g（０.１３モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン（和光純薬(株)製、試薬特級）６２５.２g（６.０モル）を２時間かけて滴下した。滴下終了後、８０℃で１時間保った。その後、８０℃の蒸留水６１８.２gを添加し、１５分間撹拌後５分間静置した。２層に分離したフラスコ内液の下層を別のフラスコに移し、同様の操作を７回繰り返した後、下層に溶解した蒸留水を減圧蒸留して留去し、ポリアミノ組成物Ｅ１１１７.３gを得た。ポリアミノ組成物Ｅの粘度は６６mPa・s/25℃、未反応ＭＸＤＡ量は０.７wt%であった。
【００２３】
合成例６
合成例１と同様のフラスコに、１,３-ＢＡＣ８５３.２g（６.０モル）とリチウムアミド３.０g（０.１３モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン６２５.２g（６.０モル）を２時間かけて滴下した。滴下終了後、８０℃で１時間保った。その後、８０℃の蒸留水６４５.２gを添加し、合成例４と同様の操作を行い、ポリアミノ組成物Ｆ１１２６.２gを得た。ポリアミノ組成物Ｆの粘度は８０mPa・s/25℃、未反応１,３-ＢＡＣ量は０.６wt%であった。
【００２４】
実施例１
合成例１で示した変性ポリアミノ化合物Ａと合成例５で示したポリアミノ組成物Ｅを１：１の重量比で混合し、エポキシ樹脂硬化剤Ｇを得た。エポキシ樹脂硬化剤Ｇの粘度は３２９mPa・s/25℃、未反応ＭＸＤＡ量は１５.４wt%であった。
エポキシ樹脂硬化剤ＧとビスフェノールＡ型液状エポキシ樹脂（商品名：エポコート８２８、ジャパンエポキシレジン(株)製）を表１に示す割合で配合しエポキシ樹脂組成物を調製した。得られたエポキシ樹脂組成物を２３℃、５０%RH条件下で硬化させ、硬化塗膜および硬化物を作製し、性能評価を行った。評価結果を表１に示す。
【００２５】
実施例２
合成例２で示した変性ポリアミノ化合物Ｂと合成例５で示したポリアミノ組成物Ｅを１：１の重量比で混合し、エポキシ樹脂硬化剤Ｈを得た。エポキシ樹脂硬化剤Ｈの粘度は８０６mPa・s/25℃、未反応ＭＸＤＡ量は２４.５wt%であった。
エポキシ樹脂硬化剤Ｇの代わりにエポキシ樹脂硬化剤Ｈを使用した以外は実施例１と同様にエポキシ樹脂組成物を調製し、該樹脂組成物から得られた硬化塗膜および硬化物の性能評価を行った。評価結果を表１に示す。
【００２６】
実施例３
合成例３で示した変性ポリアミノ化合物Ｃと合成例６で示したポリアミノ組成物Ｆを１：１の重量比で混合し、エポキシ樹脂硬化剤Ｉを得た。エポキシ樹脂硬化剤Ｉの粘度は５３５mPa・s/25℃、未反応１,３-ＢＡＣ量は１５.９wt%であった。
エポキシ樹脂硬化剤Ｇの代わりにエポキシ樹脂硬化剤Ｉを表２に記載の割合で使用した以外は実施例１と同様にエポキシ樹脂組成物を調製し、該樹脂組成物から得られた硬化塗膜および硬化物の性能評価を行った。評価結果を表２に示す。
【００２７】
実施例４
合成例４で示した変性ポリアミノ化合物Ｄと合成例６で示したポリアミノ組成物Ｆを１：１の重量比で混合し、エポキシ樹脂硬化剤Ｊを得た。エポキシ樹脂硬化剤Ｊの粘度は１０４０mPa・s/25℃、未反応１,３-ＢＡＣ量は２５.５wt%であった。
エポキシ樹脂硬化剤Ｇの代わりにエポキシ樹脂硬化剤Ｊを表２に記載の割合で使用した以外は実施例１と同様にエポキシ樹脂組成物を調製し、該樹脂組成物から得られた硬化塗膜および硬化物の性能評価を行った。評価結果を表２に示す。
【００２８】
比較例１〜４
合成例１〜４で得られた変性ポリアミノ化合物Ａ〜Ｄをエポキシ樹脂硬化剤として使用した以外は実施例１と同様にエポキシ樹脂組成物を調製し、該樹脂組成物から得られた硬化塗膜および硬化物の性能評価を行った。エポキシ樹脂との配合割合および評価結果を表１および表２に示す。
【００２９】
【表１】
【表２】
エポキシ樹脂硬化塗膜性能評価、エポキシ樹脂硬化物物性評価およびエポキシ樹脂硬化物接着性評価は以下の方法で行った。
〈硬化塗膜性能評価〉
硬化塗膜作製方法：エポキシ樹脂組成物を鋼板に２００μの厚さに塗装した。層間密着性は下層を塗装した１日後に上層を塗装した。
外観：７日硬化後の塗膜外観を目視（光沢、透明性、平滑性）および指触（乾燥性）により評価した。
層間密着性：１＋７日硬化後の塗膜をＪＩＳ Ｋ ５４００のＸカットテープ法を参考に評価した。
耐水性：１、４および７日硬化後の塗膜上に水滴を滴下し、１日後の塗膜の変化を目視により評価した。
耐薬品性：７日硬化後の塗装鋼板を各薬品に２３℃で７日間浸漬し、塗膜の変化を目視により評価した。なお、塩水噴霧はＪＩＳ Ｋ ５４００に準拠した。
評価：次の４段階で評価した。
◎：優秀 ○：良好 △：やや不良 ×：不良
〈硬化物物性評価〉
引張強度・弾性率：ＪＩＳ Ｋ ７１１３に準拠した。
曲げ強度・弾性率：ＪＩＳ Ｋ ７１７１に準拠した。
圧縮強度・弾性率：ＪＩＳ Ｋ ７１８１に準拠した。
〈硬化物接着性評価〉
引張せん断接着強度：ＪＩＳ Ｋ ６８５０に準拠した。
曲げ接着強度：ＪＩＳ Ａ ６０２４に準拠した。
【００３２】
【発明の効果】
以上の実施例から明らかなように、本発明の変性ポリアミノ化合物とポリアミノ組成物との混合物からなるポリアミノ系エポキシ樹脂硬化剤は低粘度で、未反応ポリアミノ化合物含有量が低く、該エポキシ樹脂硬化剤を含むエポキシ樹脂組成物は、良好なエポキシ樹脂硬化物性能を与える。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyamino epoxy resin curing agent comprising a mixture of a modified polyamino compound and a polyamino composition mainly composed of a polyamino compound having a specific structure in a specific range, an epoxy resin composition containing the epoxy resin curing agent, The present invention relates to a cured epoxy resin obtained by curing an epoxy resin composition.
[0002]
[Prior art]
It is well known that various polyamino compounds are widely used as epoxy resin curing agents and their raw materials. These polyamino compounds are rarely used as an epoxy resin curing agent as they are, and usually the reactivity of each amino group, that is, according to the purpose of improving safety and hygiene, improving workability, improving cured product performance, In most cases, it is used after modification suitable for characteristics resulting from active hydrogen. Epoxy resin compositions using these epoxy resin hardeners are especially used in the paint field such as anticorrosion paints for ships, bridges, land and sea iron structures, lining, reinforcement and repair of concrete structures, flooring of buildings, water and sewage systems Widely used in civil engineering and construction fields such as equipment lining, paving materials, and adhesives.
[0003]
Typical polyamino compounds include aliphatic polyamino compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, and other aliphatic polyamino compounds having an aromatic ring such as xylylenediamine. Alicyclic polyamino compounds such as mensendiamine, isophoronediamine, bis (aminomethyl) cyclohexane, N-aminomethylpiperazine, etc. Aromatic polyamino compounds such as phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and other polyethers Examples thereof include a polyamino compound having a skeleton and a polyamino compound having a norbornane skeleton.
[0004]
As a typical modification method of a polyamino compound, (1) modification by a Mannich reaction between a phenolic compound and an aldehyde compound, (2) modification by a reaction with an epoxy compound, (3) reaction by a compound having a carboxyl group Modification, (4) Modification by Michael addition reaction with an acrylic compound, and (5) Modification by a combination thereof.
[0005]
The modification ratio (degree of modification) of the polyamino compound is generally selected in such a range that the resulting modified polyamino compound has an amino group having active hydrogen derived from the polyamino compound. However, when the modification ratio is low, the viscosity of the modified polyamino compound is low, but since the content of unreacted (unmodified) polyamino compound is high, sufficient epoxy resin curing can be achieved when used as an epoxy resin curing agent. Physical performance may not be obtained. On the other hand, when the modification ratio is high, the content of the unreacted polyamino compound is low, but the viscosity is high. Therefore, it is necessary to lower the viscosity by adding a solvent or a diluent for the purpose of improving workability. The addition of a solvent is desired to be avoided due to environmental problems, and the addition of a diluent needs to be limited in order to cause a decrease in the performance of the cured epoxy resin.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a polyamino type epoxy resin curing agent having a low viscosity, a low content of unreacted polyamino compound, and good epoxy resin cured product performance, an epoxy resin composition containing the epoxy resin curing agent, and the epoxy resin It is to provide a cured epoxy resin obtained by curing a composition.
[0007]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that a polyamino epoxy resin curing agent comprising a mixture of a modified polyamino compound and a polyamino composition mainly composed of a polyamino compound having a specific structure uses the modified polyamino compound as an epoxy resin curing agent. The epoxy resin composition containing a modified polyamino compound as an epoxy resin curing agent is low in viscosity and low in unreacted polyamino compound content, and the epoxy resin composition containing the polyamino epoxy resin curing agent The present inventors have found that an excellent cured epoxy resin can be obtained without impairing the performance of the cured epoxy resin obtained by curing the composition.
[0008]
That is, the present invention relates to a modified polyamino compound having as a raw material a polyamino compound A having at least two amino groups in the molecule and having active hydrogen derived from the amino group, and a polyamino compound represented by the formula (1): A polyamino composition obtained by an addition reaction between compound B and styrene and having as a main component a polyamino compound C, which is at least one selected from the adducts represented by the formula (2) and having different side chain groups. A polyamino epoxy resin curing agent comprising a mixture is provided.
Furthermore, this invention provides the epoxy resin composition containing this epoxy resin hardening | curing agent, and the epoxy resin hardened | cured material which hardened this epoxy resin composition.
[Chemical 3]
DETAILED DESCRIPTION OF THE INVENTION
The polyamino compound A used in the present invention is a compound having at least two amino groups in the molecule and having active hydrogen derived from the amino group, and specifically includes ethylenediamine, diethylenetriamine, triethylene. Aliphatic polyamino compounds such as ethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexamethylenediamine, aliphatic polyamino compounds having an aromatic ring such as xylylenediamine, mensendiamine, isophoronediamine, bis (aminomethyl) cyclohexane , Alicyclic polyamino compounds such as N-aminomethylpiperazine, aromatic polyamino compounds such as phenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone, polyether skeleton polyamino compounds, norbornane skeleton polyamines Roh compounds, and the like. These are used alone or as a mixture.
[0010]
The modified polyamino compound of the present invention is obtained by modifying the polyamino compound A into the following modification methods: (1) modification by Mannich reaction between a phenolic compound and an aldehyde compound, (2) modification by reaction with an epoxy compound, ( 3) Modification by reaction with a compound having a carboxyl group, (4) Modification by Michael addition reaction with an acrylic compound, and (5) Modification by combination thereof.
[0011]
The modification ratio of the polyamino compound A of the present invention is not particularly limited as long as the resulting modified polyamino compound contains an amino group having active hydrogen.
[0012]
Examples of the polyamino compound B represented by the formula (1) used in the present invention include orthoxylylenediamine, metaxylylenediamine, paraxylylenediamine, 1,2-bis (aminomethyl) cyclohexane, 1,3-bis. (Aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane and the like can be mentioned. Of these, metaxylylenediamine and 1,3-bis (aminomethyl) cyclohexane are particularly preferred.
[0013]
The polyamino compound C used in the present invention is obtained by an addition reaction between the polyamino compound B and styrene, and is represented by at least one selected from the adducts represented by the formula (2) and having different side chain group structures. A compound. Here, each compound having a different structure of the side chain group in the formula (2) is an adduct in which all of R1, R2 and R3 are hydrogen, any two are hydrogen, and the remaining one is a phenethyl group. , Any two are phenethyl groups, the other is hydrogen, and both are phenethyl groups.
In the present invention, these adducts are used alone or as a mixture.
[0014]
In the present invention, when synthesizing the polyamino compound C, it is preferable to use a catalyst exhibiting strong basicity. For example, there are alkali metals, alkali metal amides, alkylated alkali metals, etc., preferably alkali metal amides (general formula MNRR ′: M is an alkali metal, N is nitrogen, R and R ′ are each independently hydrogen or alkyl A lithium amide (LiNH 2 ).
[0015]
The epoxy resin curing agent of the present invention is a mixture of the modified polyamino compound and a polyamino composition containing polyamino compound C as a main component. The mixing weight ratio of the modified polyamino compound and the polyamino composition is selected in the range of 2: 8 to 8: 2, particularly preferably in the range of 4: 6 to 6: 4. When the mixing weight ratio of the modified polyamino compound is lower than 2, the performance of the cured epoxy resin may be impaired when the modified polyamino compound is used as an epoxy resin curing agent. The agent is not preferable because the viscosity is not sufficiently lowered and the content of the unreacted polyamino compound is not sufficiently reduced.
[0016]
The epoxy resin composition of the present invention comprises the epoxy resin curing agent and an epoxy resin. As the epoxy resin used in the composition, a bisphenol A type epoxy resin or a bisphenol F type epoxy resin is used alone or in combination, but the glycidyl group reacts with the active hydrogen of the epoxy resin curing agent of the present invention. Any epoxy resin can be used as long as it has a low molecular weight, and is not limited thereto. Furthermore, the epoxy resin composition of the present invention is used for other components such as fillers, modifying components such as plasticizers, flow control components such as diluents and thixotropic agents, pigments, leveling agents and tackifiers. It can be added and used accordingly. By curing the epoxy resin composition of the present invention, various cured products such as a cured coating film can be obtained.
[0017]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0018]
<Synthesis of modified polyamino compounds>
Synthesis example 1
In a 2 liter flask equipped with a stirrer, thermometer, nitrogen inlet tube, dropping funnel, and cooling tube, metaxylylenediamine (Mitsubishi Gas Chemical Co., Ltd., hereinafter referred to as MXDA) 612.9 g (4.5 mol) And phenol (manufactured by Wako Pure Chemical Industries, Ltd., first grade reagent) 423.45 g (4.5 mol) were charged, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. While maintaining at 80 ° C., 243.3 g (3.0 mol) of formalin (manufactured by Mitsubishi Gas Chemical Co., Inc., 37% aqueous solution containing 8% methanol) was added dropwise over 1.5 hours. After completion of the dropwise addition, the temperature was raised to 100 ° C. and the reaction was performed for 1.5 hours. Thereafter, the temperature was raised to 150 ° C. over 2 hours while distilling off the generated water, and the reaction was carried out at the same temperature for 1 hour to obtain 1068.2 g of modified polyamino compound A by Mannich reaction. The modified polyamino compound A had a viscosity of 2450 mPa · s / 25 ° C. and an unreacted MXDA amount of 30.0 wt%.
[0019]
Synthesis example 2
MXDA 817.2 g (6.0 mol) was charged into the same flask as in Synthesis Example 1, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. While maintaining at 80 ° C., 456.0 g of bisphenol A diglycidyl ether (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 828, epoxy equivalent: 190 g / eq) was added dropwise over 2 hours. After completion of the dropwise addition, the temperature was raised to 100 ° C. and the reaction was carried out for 2 hours to obtain 1264.8 g of a modified polyamino compound B. The viscosity of the modified polyamino compound B was 9840 mPa · s / 25 ° C., and the amount of unreacted MXDA was 48.4 wt%.
[0020]
Synthesis example 3
The same as in Synthesis Example 1 except that MXDA was replaced with 639.9 g (4.5 mol) of 1,3-bis (aminomethyl) cyclohexane (Mitsubishi Gas Chemical Co., Ltd., hereinafter referred to as 1,3-BAC). The synthesis was carried out under the conditions as described above to obtain 1091.8 g of a modified polyamino compound C109. The viscosity of the modified polyamino compound C was 4360 mPa · s / 25 ° C., and the amount of unreacted 1,3-BAC was 31.2 wt%.
[0021]
Synthesis example 4
Synthesis was carried out under the same conditions as in Synthesis Example 2 except that MXDA was replaced with 853.2 g (6.0 mol) of 1,3-BAC to obtain 1298.4 g of a modified polyamino compound D. The modified polyamino compound D had a viscosity of 12,500 mPa · s / 25 ° C. and an unreacted 1,3-BAC content of 50.3 wt%.
[0022]
<Synthesis of polyamino composition>
Synthesis example 5
In a 2 liter flask equipped with a stirrer, thermometer, nitrogen inlet tube, dropping funnel and condenser, MXDA 817.2 g (6.0 mol) and lithium amide (Merck, reagent) 2.9 g (0.13 mol) And heated to 80 ° C. with stirring under a nitrogen stream. While maintaining the temperature at 80 ° C., 625.2 g (6.0 mol) of styrene (manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade) was added dropwise over 2 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour. Thereafter, 618.2 g of distilled water at 80 ° C. was added, and the mixture was stirred for 15 minutes and allowed to stand for 5 minutes. The lower layer of the liquid in the flask separated into two layers was transferred to another flask, and the same operation was repeated seven times. Then, distilled water dissolved in the lower layer was distilled off under reduced pressure to obtain a polyamino composition E1117.3 g. It was. Polyamino composition E had a viscosity of 66 mPa · s / 25 ° C. and an unreacted MXDA amount of 0.7 wt%.
[0023]
Synthesis Example 6
A flask similar to that in Synthesis Example 1 was charged with 853.2 g (6.0 mol) of 1,3-BAC and 3.0 g (0.13 mol) of lithium amide, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. . While maintaining the temperature at 80 ° C., 625.2 g (6.0 mol) of styrene was added dropwise over 2 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour. Thereafter, 645.2 g of distilled water at 80 ° C. was added, and the same operation as in Synthesis Example 4 was performed to obtain a polyamino composition F1126.2 g. The viscosity of the polyamino composition F was 80 mPa · s / 25 ° C., and the amount of unreacted 1,3-BAC was 0.6 wt%.
[0024]
Example 1
The modified polyamino compound A shown in Synthesis Example 1 and the polyamino composition E shown in Synthesis Example 5 were mixed at a weight ratio of 1: 1 to obtain an epoxy resin curing agent G. The viscosity of the epoxy resin curing agent G was 329 mPa · s / 25 ° C., and the amount of unreacted MXDA was 15.4 wt%.
Epoxy resin curing agent G and bisphenol A type liquid epoxy resin (trade name: Epocoat 828, manufactured by Japan Epoxy Resin Co., Ltd.) were blended in the ratio shown in Table 1 to prepare an epoxy resin composition. The obtained epoxy resin composition was cured under conditions of 23 ° C. and 50% RH to produce a cured coating film and a cured product, and performance evaluation was performed. The evaluation results are shown in Table 1.
[0025]
Example 2
The modified polyamino compound B shown in Synthesis Example 2 and the polyamino composition E shown in Synthesis Example 5 were mixed at a weight ratio of 1: 1 to obtain an epoxy resin curing agent H. The viscosity of the epoxy resin curing agent H was 806 mPa · s / 25 ° C., and the amount of unreacted MXDA was 24.5 wt%.
Except that the epoxy resin curing agent H was used instead of the epoxy resin curing agent G, an epoxy resin composition was prepared in the same manner as in Example 1, and the performance evaluation of the cured coating film and cured product obtained from the resin composition was performed. went. The evaluation results are shown in Table 1.
[0026]
Example 3
The modified polyamino compound C shown in Synthesis Example 3 and the polyamino composition F shown in Synthesis Example 6 were mixed at a weight ratio of 1: 1 to obtain an epoxy resin curing agent I. The viscosity of the epoxy resin curing agent I was 535 mPa · s / 25 ° C., and the amount of unreacted 1,3-BAC was 15.9 wt%.
An epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy resin curing agent I was used in the ratio shown in Table 2 instead of the epoxy resin curing agent G, and a cured coating film obtained from the resin composition The performance of the cured product was evaluated. The evaluation results are shown in Table 2.
[0027]
Example 4
The modified polyamino compound D shown in Synthesis Example 4 and the polyamino composition F shown in Synthesis Example 6 were mixed at a weight ratio of 1: 1 to obtain an epoxy resin curing agent J. The viscosity of the epoxy resin curing agent J was 1040 mPa · s / 25 ° C., and the amount of unreacted 1,3-BAC was 25.5 wt%.
An epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy resin curing agent J was used in the ratio shown in Table 2 instead of the epoxy resin curing agent G, and a cured coating film obtained from the resin composition The performance of the cured product was evaluated. The evaluation results are shown in Table 2.
[0028]
Comparative Examples 1-4
An epoxy resin composition was prepared in the same manner as in Example 1 except that the modified polyamino compounds A to D obtained in Synthesis Examples 1 to 4 were used as an epoxy resin curing agent, and a cured coating film obtained from the resin composition The performance of the cured product was evaluated. Tables 1 and 2 show the blending ratio with the epoxy resin and the evaluation results.
[0029]
[Table 1]
[Table 2]
The epoxy resin cured coating film performance evaluation, the epoxy resin cured product property evaluation, and the epoxy resin cured product adhesion evaluation were performed by the following methods.
<Evaluation of cured coating film performance>
Cured coating film preparation method: The epoxy resin composition was applied to a steel plate to a thickness of 200 μm. Interlayer adhesion was applied one day after the lower layer was coated.
Appearance: The appearance of the coating film after curing for 7 days was evaluated visually (gloss, transparency, smoothness) and finger touch (dryness).
Interlayer adhesion: The coating film after curing for 1 + 7 days was evaluated with reference to the JIS K 5400 X-cut tape method.
Water resistance: A drop of water was dropped on the coating film cured for 1, 4 and 7 days, and the change of the coating film after 1 day was visually evaluated.
Chemical resistance: The coated steel sheet after 7 days of curing was immersed in each chemical at 23 ° C. for 7 days, and the change of the coating film was visually evaluated. The salt spray was in accordance with JIS K 5400.
Evaluation: Evaluated in the following four stages.
◎: Excellent ○: Good △: Slightly poor ×: Poor <Evaluation of cured material properties>
Tensile strength / elastic modulus: compliant with JIS K7113.
Bending strength and elastic modulus: compliant with JIS K 7171.
Compressive strength / elastic modulus: compliant with JIS K 7181.
<Evaluation of cured product adhesion>
Tensile shear bond strength: compliant with JIS K 6850.
Bending adhesive strength: compliant with JIS A 6024.
[0032]
【The invention's effect】
As is clear from the above examples, the polyamino epoxy resin curing agent comprising the mixture of the modified polyamino compound of the present invention and the polyamino composition has a low viscosity and a low content of unreacted polyamino compound, and the epoxy resin curing agent is low. The epoxy resin composition containing contains good epoxy resin cured product performance.
Claims (4)
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Cited By (1)
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| JP2004263177A (en) * | 2003-02-13 | 2004-09-24 | Mitsubishi Gas Chem Co Inc | Curing agent for low-temperature curing epoxy resin and epoxy resin composition |
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| KR20070056044A (en) * | 2004-06-21 | 2007-05-31 | 훈츠만 어드밴스트 머티리얼스(스위처랜드) 게엠베하 | Curing agents for epoxy resins |
| JP4910682B2 (en) * | 2005-12-28 | 2012-04-04 | 三菱瓦斯化学株式会社 | Epoxy resin curing agent and epoxy resin composition |
| JP4910683B2 (en) * | 2005-12-28 | 2012-04-04 | 三菱瓦斯化学株式会社 | Epoxy resin curing agent and epoxy resin composition |
| EP2822985B1 (en) * | 2012-03-09 | 2016-11-30 | Construction Research & Technology GmbH | Amine curable epoxy resin composition |
| JP7177580B2 (en) * | 2016-11-24 | 2022-11-24 | 三菱瓦斯化学株式会社 | Epoxy resin curing agent, epoxy resin composition and cured product thereof |
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| JP2004263177A (en) * | 2003-02-13 | 2004-09-24 | Mitsubishi Gas Chem Co Inc | Curing agent for low-temperature curing epoxy resin and epoxy resin composition |
| JP4596123B2 (en) * | 2003-02-13 | 2010-12-08 | 三菱瓦斯化学株式会社 | Low temperature curing type epoxy resin curing agent and epoxy resin composition |
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