JP3650994B2 - Aqueous vinyl-modified epoxy resin, production method thereof, and aqueous coating agent - Google Patents
Aqueous vinyl-modified epoxy resin, production method thereof, and aqueous coating agent Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、ビニル変性エポキシ樹脂水性物、その製造方法および当該ビニル変性エポキシ樹脂を含有してなる水性被覆剤に関する。
【０００２】
【従来の技術】
従来、水性塗料により得られる塗膜は耐食性に劣るとされていたが、かかる耐食性を改良したものとして、脂肪酸変性エポキシエステルの存在下に、ビニル単量体を重合して得られるビニル変性エポキシエステルが開発された。当該ビニル変性エポキシエステルは、その構成成分としてエポキシ樹脂を用いているため高い耐食性を有し、脂肪酸エステル成分により常温乾燥が可能であり、しかもビニル単量体成分の選択により水性化が可能である。
【０００３】
しかし、水性塗料の適用分野が拡大するに従がい、当該塗膜に対する要求性能も高まり、耐食性や耐水性の一段のレベルアップや、高い初期塗膜硬度が求められている。例えば、従来のビニル変性エポキシエステルでは初期塗膜硬度が低く、当該樹脂中の脂肪酸成分の酸化重合により徐々に塗膜硬度が上昇し、目的硬度に到達するのに数日を要するため、塗膜形成初期の傷つきが問題となっていた。また、従来知られているビニル変性エポキシエステルでは、当該樹脂から調製された黒色塗膜が浸水時に白化する現象（以下、耐水白化という）も問題となっていた。かかる耐水白化は、ビニル変性エポキシエステル中の脂肪酸成分の比率を増加させることにより改善されるが、一方で塗膜硬度や耐食性が低下しやすい。
【０００４】
【発明が解決しようとする課題】
本発明は、耐食性の低下がなく、初期塗膜硬度が高く、黒色塗膜における耐水白化の生じにくいビニル変性エポキシ樹脂水性物を提供するとともに、当該ビニル変性エポキシ樹脂水性物からなる水性被覆剤を提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明者は、前記課題を解決すべく鋭意検討を重ねた結果、脂肪酸類を使用しない重合性不飽和基含有変性エポキシ樹脂の存在下で、特定のビニル単量体を重合してなる反応生成物の水分散塩または水溶液が、前記課題を解決できることを見出し、本発明を完成するに到った。
【０００６】
すなわち、本発明はビスフェノール型エポキシ樹脂（１ａ）、グリシジル基含有ビニルモノマー（１ｂ）およびアミン類（１ｃ）を反応させてなる重合性不飽和基含有変性エポキシ樹脂（１）と、カルボキシル基含有ビニル単量体（２）とを共重合させてなる共重合体（Ａ）を、塩基性化合物により中和して水中に分散ないしは溶解せしめてなることを特徴とするビニル変性エポキシ樹脂水性物；当該水性物の製造方法；ならびに当該水性物を含有してなる水性被覆剤に関する。
【０００７】
【発明の実施の形態】
本発明で用いる前記共重合体（Ａ）は、ビスフェノール型エポキシ樹脂（１ａ）、グリシジル基含有ビニルモノマー（１ｂ）およびアミン類（１ｃ）を反応させてなる重合性不飽和基含有変性エポキシ樹脂（１）と、カルボキシル基含有ビニル単量体（２）とを共重合させてなるものである。また共重合体（Ａ）は、前記構成成分である（１ａ）、（１ｂ）、（１ｃ）および（２）に加えて、必要に応じ、反応可能な成分（１ｄ）や、当該単量体（２）と共重合しうる他のビニル単量体（３）を追加構成成分とすることが出来る。
【０００８】
重合性不飽和基含有変性エポキシ樹脂（１）は、前記のようにビスフェノール型エポキシ樹脂（１ａ）、グリジシル基含有重合性ビニルモノマー（１ｂ）、ならびにアミン類（１ｃ）および必要により反応可能な成分（１ｄ）からなる各構成成分からなる反応生成物である。すなわち、ビスフェノール型エポキシ樹脂（１ａ）中のエポキシ基がアミン類（１ｃ）により開環すると同時に、当該エポキシ樹脂（１ａ）中にアミノ基が導入されることで未変性エポキシ樹脂（１ａ）の本来の性能である密着性等がさらに向上すると考えられる。またグリジシル基含有重合性ビニルモノマー（１ｂ）がアミン類（１ｃ）を介してビスフェノール型エポキシ樹脂（１ａ）中のエポキシ基と反応するため、該エポキシ樹脂（１ａ）中に重合性不飽和基が導入され、共重合性が付与される。
【０００９】
本発明に使用するビスフェノール型エポキシ樹脂（１ａ）としては各種公知のものが使用できるが、例えばビスフェノール類とエピクロルヒドリンまたはβ−メチルエピクロルヒドリン等のハロエポキシド類の反応生成物等が挙げられる。該ビスフェノール類としては、フェノールまたは２，６−ジハロフェノールと、ホルムアルデヒド、アセトアルデヒド、アセトン、アセトフェノン、シクロヘキサノン、ベンゾフェノン等のアルデヒド類もしくはケトン類との反応物、ジヒドロキシフェニルスルフィドの過酸化物、ハイドロキノン同士のエーテル化反応物、脂肪族多価アルコールのグリシジルエーテル、脂肪族多塩基酸のグリシジルエーテル等があげられる。当該エポキシ樹脂は、いずれか一種を単独で使用できる他、二種以上を適宜に併用することもできる。当該ビスフェノール型エポキシ樹脂（１ａ）成分のエポキシ当量は、得られる共重合体（Ａ）の分子量や製造時の作業性などを考慮して、３０００以下とするのが好ましい。エポキシ当量が３０００を超える場合は、得られる共重合体（Ａ）の分子量が増大し、ゲル化しやすくなる不利がある。
【００１０】
グリシジル基含有ビニルモノマー（１ｂ）としては、グリシジル基と重合性ビニル基を分子内に含有する各種公知の化合物であれば特に制限なく使用できる。具体的には、例えばグリシジル（メタ）アクリレート、β−メチルグリシジル（メタ）アクリレート、（メタ）アリルグリシジルエーテル等があげられる。
【００１１】
アミン類（１ｃ）としては、各種公知のアミン類が特に制限なく使用できる。例えば、アルカノールアミン類、脂肪族アミン類、芳香族アミン類、脂環族アミン類、芳香核置換脂肪族アミン類等があげられ、これらは１種または２種以上を適宜選択して使用できる。アミン類（１ｃ）の種類を具体的に示すと、アルカノールアミン類としては、例えばジエタノールアミン、ジイソプロパノールアミン、ジ−２−ヒドロキシブチルアミン、Ｎ−メチルエタノールアミン、Ｎ−エチルエタノールアミン、Ｎ−ベンジルエタノールアミン等があげられる。また、脂肪族アミン類としては、例えばエチルアミン、プロピルアミン、ブチルアミン、ヘキシルアミン、ラウリルアミン、ステアリルアミン、パルミチルアミン、オレイルアミン、エルシルアミン等の一級アミン類やジエチルアミン、ジプロピルアミン、ジブチルアミン等の二級アミン類があげられる。また、芳香族アミン類としては、例えばトルイジン類、キシリジン類、クミジン（イソプロピルアニリン）類、ヘキシルアニリン類、ノニルアニリン類、ドデシルアニリン類等があげられる。脂環族アミン類としてはシクロペンチルアミン類、シクロヘキシルアミン類、ノルボルニルアミン類があげられる。また、芳香核置換脂肪族アミン類としては、例えばベンジルアミン、フェネチルアミン等があげられる。
【００１２】
また、重合性不飽和基含有変性エポキシ樹脂（１）には、前記のように追加構成成分として、反応可能な化合物（１ｄ）を使用しうる。重合性不飽和基含有変性エポキシ樹脂（１）を上記化合物（１ｄ）で変性（高分子量化）することにより、得られる樹脂水性物の水への分散性を調整したり、得られる塗膜の加工性を一層向上させうる。当該化合物（１ｄ）としては、１価〜３価の有機酸、１価〜４価のアルコール、イソシアネート化合物等があげられる。１価〜３価の有機酸としては、脂肪族、脂環族または芳香族の各種公知のカルボン酸が使用でき、例えばダイマー酸、トリメリット酸等があげられる。１価〜４価のアルコールとしては、脂肪族、脂環族または芳香族の各種公知のアルコールが使用でき、例えばネオペンチルグリコール、トリメチロールプロパン、ペンタエリスリトール等があげられる。イソシアネート化合物としては、芳香族、脂肪族または脂環族の各種公知のポリイソシアネートが使用でき、例えばトリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート等があげられる。
【００１３】
重合性不飽和基含有変性エポキシ樹脂（１）の製造方法は特に限定されず、各種公知の方法を適用できるが、例えば以下の条件を採用し得る。ビスフェノール型エポキシ樹脂（１ａ）に対するグリシジル基含有ビニルモノマー（１ｂ）、アミン類（１ｃ）および他の反応可能な化合物（１ｄ）の使用量割合は、それぞれ以下の範囲とされる。すなわち、該ビスフェノール型エポキシ樹脂（１ａ）とグリシジル基含有ビニルモノマー（１ｂ）に含まれるエポキシ基の総量１００当量に対して、アミン類（１ｃ）のアミノ基に由来する活性水素の当量が９０〜１１０当量程度となるように用いるのが好ましい。また、ビスフェノール型エポキシ樹脂（１ａ）のエポキシ基１００当量に対してグリシジル基含有ビニルモノマー（１ｂ）のエポキシ当量が1〜２５当量程度となるように用いるのが好ましい。グリシジル基含有ビニルモノマー（１ｂ）のエポキシ当量が１に満たない場合、本発明の変性エポキシ樹脂水性物の貯蔵安定性が低下し、また２５を超える場合には当該変性エポキシ樹脂（１）が製造時にゲル化する傾向にある。また、他の反応可能な化合物（１ｄ）は本発明の効果を損なわない範囲で、必要に応じ使用できる。
【００１４】
重合性不飽和基含有変性エポキシ樹脂（１）は、下記の有機溶剤の存在下に、前記各成分を加熱することにより容易に製造できる。反応温度は通常６０〜２００℃程度であるが、反応温度が低すぎると未反応のエポキシ基が残存する傾向にあることから８０℃以上が好ましい。一方、反応温度が高すぎると変性エポキシ樹脂（１）中のエポキシ基と他成分中の水酸基との開環反応や、エポキシ基同士の開環反応に起因して反応生成物がゲル化しやすくなるため、１５０℃以下とするのが好ましい。また、反応時間は反応温度に依存するが、前記温度条件下では３〜１０時間とするのがよい。
【００１５】
当該有機溶剤としては、最終的に得られるビニル変性エポキシ樹脂の水性化の観点から親水性溶剤を使用するのが望ましく、具体的にはプロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノn−ブチルエーテル、プロピレングリコールモノt−ブチルエーテル、メチルセロソルブ、エチルセロソルブ、ｎ−ブチルセロソルブ、t−ブチルセロソルブ、イソプロピルアルコール、ブチルアルコールなどがあげられる。
【００１６】
本発明で使用する共重合体（Ａ）は、上記のようにして得られた重合性不飽和基含有変性エポキシ樹脂（１）と、カルボキシル基含有ビニル単量体（２）および必要に応じ当該単量体（２）と共重合しうる他のビニル単量体（３）とを共重合させることにより製造する。本発明における共重合体（Ａ）は、ビニルグラフト−アミン変性エポキシ樹脂に相当する。本発明では、重合性不飽和基含有変性エポキシ樹脂（１）の重合性不飽和基と、カルボキシル基含有ビニル単量体（２）および必要により他の単量体（３）とを、共重合させてグラフト体を製造することが重要である。かかるグラフト化により、前記エポキシ樹脂（１ａ）の本来の性能である耐食性、密着性を高度に維持しつつ、水中に安定に分散または溶解しうる共重合体（Ａ）を収得できる。
【００１７】
前記重合性不飽和基含有変性エポキシ樹脂（１）と共重合させるカルボキシル基含有ビニル単量体（２）としては、例えばアクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、フマル酸、イタコン酸等のカルボキシル基含有ビニル単量体があげられる。また、カルボキシル基含有ビニル単量体（２）と共重合しうる任意成分である他のビニル単量体（３）としては、例えばアクリル酸メチル、アクリル酸エチル、アクリル酸n−プロピル、アクリル酸n−ブチル、アクリル酸イソブチル、アクリル酸ｔｅｒｔ−ブチル、アクリル酸２−エチルヘキシル等のアクリル酸エステル類；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸n−プロピル、メタクリル酸n−ブチル、メタクリル酸イソブチル、メタクリル酸ｔｅｒｔ−ブチル、メタクリル酸２−エチルヘキシル等のメタクリル酸エステル類；スチレン、ビニルトルエン、α−メチルスチレン等のスチレン系ビニル単量体；その他、酢酸ビニル、アクリル酸β−ヒドロキシエチル、アクリル酸グリシジル、メタクリル酸グリシジル、アクリルアミド、Ｎ，Ｎ-ジエチルメタクリルアミド、アクリロニトリル、メタクリロニトリル等があげられる。これらビニル単量体（２）および（３）は、いずれも一種を単独で使用でき、または二種以上を併用できる。
【００１８】
前記カルボキシル基含有ビニル単量体（２）は、得られるビニル変性エポキシ樹脂の水性化（安定に水分散または溶解）を容易にするために必須使用される。そのため、当該カルボキシル基含有ビニル単量体（２）の使用量は、得られるビニル変性エポキシ樹脂の水性化の観点から決定され、ビニル変性エポキシ樹脂の固形分酸価が１５以上、さらには２０以上になるよう調節するのが好ましい。一方、ビニル変性エポキシ樹脂に良好な耐水性や耐食性を付与するためはビニル変性エポキシ樹脂の固形分酸価が４５以下、さらには４０以下になるよう当該使用量を調節するのが好ましい。なお、任意成分である他のビニル単量体（３）をカルボキシル基含有ビニル単量体（２）と併用する場合にも、前記と同様の観点から、これら両成分の使用量を決定でき、得られるビニル変性エポキシ樹脂の固形分酸価が前記と同様の範囲内となるよう適宜調節するのがよい。
【００１９】
重合性不飽和基含有変性エポキシ樹脂（１）と、カルボキシル基含有ビニル単量体（２）および必要により他のビニル単量体（３）との共重合に際しては、使用する重合開始剤に関して特に制限がなく、公知各種の有機過酸化物やアゾ化合物を用いることができる。例えば、ベンゾイルパーオキサイド、ｔｅｒｔ−ブチルパーオクトエイト、２，２−アゾビスイソブチロニトリル、２，２−アゾビス（２，４−ジメチルバレロニトリル）等があげられる。
【００２０】
また、当該共重合に際しては、重合様式には限定されないが、溶液重合法が好ましい。たとえば、前記のような重合開始剤の存在下で６０〜１５０℃程度の反応温度で重合できる。有機溶剤については、前記の重合性不飽和基含有変性エポキシ樹脂（１）の製造において用いたのと同様のものを使用できる。重合性不飽和基含有変性エポキシ樹脂（１）とカルボキシル基含有ビニル単量体（２）と他のビニル単量体（３）との使用重量比（（１）／〔（２）+（３）〕）は、前記の通り得られる共重合体（Ａ）の固形分酸価を考慮して適宜決定できるが、通常は９９／１〜８０／２０の範囲内とするのがよく、ビニル単量体の使用量が当該下限値より少ないと水分散性または水溶解性が不安定となり、生成物に沈殿が生じる。また、ビニル単量体が当該上限値を超えるとビニル変性エポキシ樹脂の本来の特徴である密着性、耐食性が低下しやすい。
【００２１】
こうして得られる共重合体（Ａ）は、塩基性化合物で中和され、水に溶解ないし分散させることにより、目的とするビニル変性エポキシ樹脂水性物とされる。すなわち、共重合体（Ａ）中のビニル単量体（２）由来のカルボキシル基を全部または部分中和して、当該ｐＨは７〜１０程度にするのが好ましい。中和剤である塩基性化合物としては、アンモニア、トリエチルアミン、ジメチルエタノールアミン等のアミン類、水酸化カリウム、水酸化ナトリウム等のアルカリ金属の水酸化物等を使用することができるが、塗膜からの揮散性を考慮すれば、アンモニアやアミン類が好ましい。
【００２２】
本発明のビニル変性エポキシ樹脂水性物は木材、紙、繊維、プラスチック、セラミック、鉄、非鉄金属等の各種材料に対する水性被覆剤（例えば塗料などのコーティング剤や接着剤）等として各種用途に使用できる。各種用途への適用にあたっては、水で希釈してそのまま使用できる他、必要に応じて顔料、可塑剤、溶剤、着色剤、消泡剤等を添加したり、他の水溶性または水分散性樹脂を配合することもできる。
【００２３】
【発明の効果】
本発明のビニル変性エポキシ樹脂は、従来のエポキシエステル系樹脂に匹敵する高度の耐食性を有するとともに、塗膜の初期硬度が高く、耐水性（黒色塗膜における耐水白化など）にも優れており、塗料などの各種の水性被覆剤として利用できる。
【００２４】
【実施例】
以下に実施例および比較例をあげて本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。
【００２５】
実施例１
攪拌機、冷却器、温度計及び窒素ガス導入管を備えた反応装置に、ｔｅｒｔ−ブチルセロソルブ１２０ｇ、ビスフェノールＡ型エポキシ樹脂（東都化成（株）製：エポトートＹＤ−０１４、エポキシ当量９５０）３００ｇおよびグリシジルメタクリレート５．６ｇを加え窒素気流下１００℃で溶解させた後、オクチルアミン１８．４ｇ、ジ−２−エチルへキシルアミン１７．７ｇを加え５時間反応させ、重合性不飽和基含有変性エポキシ樹脂を得た。ついで、当該反応系内に、アクリル酸１３ｇ、ｔｅｒｔ−ブチルセロソルブ４０ｇおよびｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート３ｇからなる混合物を１時間かけて滴下し４時間保温した。８０℃に冷却後、トリエチルアミン１８ｇおよび水４８０ｇを順に添加混合することにより、不揮発分３５．０％、粘度６５０ｍＰａ・ｓ、ｐＨ９．７、固形分酸価２８の水分散物を得た。
【００２６】
実施例２
実施例１と同様の反応装置に、ｔｅｒｔ−ブチルセロソルブ１２０ｇ、ビスフェノールＡ型エポキシ樹脂（東都化成（株）製：エポトートＹＤ−０１４、エポキシ当量９５０）３００ｇおよびグリシジルメタクリレート５．６ｇを加え窒素気流下１００℃で溶解させた後、オクチルアミン１８．４ｇ、ジ−２−エチルへキシルアミン１７．７ｇを加え５時間反応させ、重合性不飽和基含有変性エポキシ樹脂を得た。ついで、当該反応系内に、アクリル酸１５ｇ、スチレン１２ｇ、アクリル酸ブチル１２ｇ、ｔｅｒｔ−ブチルセロソルブ４０ｇおよびｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート３ｇからなる混合物を１時間かけて滴下し４時間保温した。８０℃に冷却後、トリエチルアミン２１ｇおよび水５４０ｇを順に添加混合することにより、不揮発分３５．０％、粘度４５０ｍＰａ・ｓ、ｐＨ９．７、固形分酸価３０の水分散物を得た。
【００２７】
実施例３
実施例１と同様の反応装置に、ｔｅｒｔ−ブチルセロソルブ１２０ｇ、ビスフェノールＡ型エポキシ樹脂（エポトートＹＤ−０１４）３００ｇ、グリシジルメタクリレート７．５ｇを加え窒素気流下１００℃で溶解させた後、オクチルアミン１８．９ｇ、モノエタノールアミン９．０ｇ、ジ−２−エチルへキシルアミン２３．６ｇを加え５時間反応させ、さらにヘキサメチレンジイソシアネート８．０ｇを加え５時間反応させ、重合性不飽和基含有変性エポキシ樹脂を得た。ついで、当該反応系内に、アクリル酸１５ｇ、スチレン６ｇ、アクリル酸ブチル６ｇ、ｔｅｒｔ−ブチルセロソルブ４０ｇおよびｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート３ｇを１時間かけて滴下し４時間保温した。８０℃に冷却後、トリエチルアミン２１ｇおよび水５６０ｇを順に添加混合することにより、不揮発分３５．０％、粘度７００ｍＰａ・ｓ、ｐＨ９．７、固形分酸価３０の水分散物を得た。
【００２８】
実施例４
実施例１と同様の反応装置に、ｔｅｒｔ−ブチルセロソルブ１２０ｇ、ビスフェノールＡ型エポキシ樹脂（エポトートＹＤ−０１４）３００ｇおよびグリシジルメタクリレート５．６ｇを加え窒素気流下１００℃で溶解させた後、オクチルアミン１８．４ｇおよびジ−２−エチルへキシルアミン１７．７ｇを加え５時間反応させ、重合性不飽和基含有変性エポキシ樹脂を得た。ついで、当該反応系内に、アクリル酸１８ｇ、スチレン４５ｇ、アクリル酸ブチル４５ｇ、ｔｅｒｔ−ブチルセロソルブ５０ｇおよびｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート３ｇからなる混合物を１時間かけて滴下し４時間保温した。８０℃に冷却後、トリエチルアミン２１ｇおよび水６６０ｇを順に添加混合することにより、不揮発分３５．０％、粘度３５０ｍＰａ・ｓ、ｐＨ９．７、固形分酸価３１の水分散物を得た。
【００２９】
比較例１
実施例１と同様の反応装置に、ｔ−ブチルセロソルブ１２０ｇ、ビスフェノールＡ型エポキシ樹脂（エポトートＹＤ−０１４）３００ｇを加え窒素気流下１００℃で溶解させた後、オクチルアミン１６．３ｇおよびジ−２−エチルへキシルアミン１５．２ｇを加え５時間反応させ、変性エポキシ樹脂を得た。ついで、当該反応系内に、アクリル酸１５ｇ、スチレン１２ｇ、アクリル酸ブチル１２ｇ、ｔｅｒｔ−ブチルセロソルブ４０ｇおよびｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート３ｇからなる混合物を１時間かけて滴下し４時間保温した。８０℃に冷却後、トリエチルアミン２１ｇおよび水５４０ｇを順に添加混合することにより、不揮発分３５．０％、粘度２５０ｍＰａ・ｓ、ｐＨ９．７、固形分酸価３２の水分散物を得た。当該水分散物は、1日後に沈殿を生じた。
【００３０】
比較例２
攪拌機、温度計、還流脱水装置及び窒素ガス導入管を付けた１リットルのガラス製フラスコ中に、ビスフェノールＡ型エポキシ樹脂（エポトートＹＤ−０１４）２００ｇ、大豆油脂肪酸９６ｇおよび炭酸水素ナトリウム０．１５ｇを入れ、窒素ガスを吹き込みながら２２０℃で加熱し、酸価が１以下になるまで付加・縮合を行い脂肪酸変性エポキシエステルを得た。得られた脂肪酸変性エポキシエステル２５０ｇおよびｔｅｒｔ−ブチルセロソルブ５０ｇを同様の反応装置に入れ、１３０℃に加熱攪拌した。ついで、当該反応系内に、スチレン１８ｇ、アクリル酸１４ｇ、ｔｅｒｔ−パーオキシベンゾエート３ｇおよびｔｅｒｔ−ブチルセロソルブ８０ｇからなる混合物を１時間かけて滴下し、更に４時間保温した。８０℃に冷却後、トリエチルアミン１９ｇおよび水４００ｇを順に添加混合することにより、不揮発分３４．８％、粘度３００ｍＰａ・ｓ、ｐＨ９．７、固形分酸価３５のビニル変性エポキシエステルの水分散物を得た。
【００３１】
実施例および比較例で得られたビニル変性エポキシ樹脂水性物を下記の配合にて水性塗料を調製し、当該塗料から得られた塗膜につき以下の方法で性能評価した。評価結果を表1に示す。
【００３２】
（水性塗料の調製）
ビニル変性エポキシ樹脂水性物４４．６ｇ、カーボンブラック１．８ｇ、リン酸亜鉛５．６ｇ、炭酸カルシウム２３．８ｇ、脱イオン水１．８ｇ及びガラスビーズ８０ｇを混合後、ペイントシェーカーにて１時間３０分練合した。その後、ビニル変性エポキシ樹脂の水分散物２３ｇを混合した後、ガラスビーズを除去し水性塗料を得た。なお、いずれのビニル変性エポキシ樹脂水性物を用いた場合にも、水性塗料のＰＷＣ（顔料重量濃度）が５７％、塗料濃度が５３．２％（溶剤量１０．２％）になるように調製した。得られた水性塗料を、脱脂ダル鋼板（ＳＰＣＣ−ＳＤ、０．８×７０×１５０ｍｍ）上に、乾燥後の膜厚が２０μｍとなるように、バーコーターにより塗布し、強制乾燥（８０℃×２０分）後、常温（２０℃、６０％Ｒ．Ｈ．）で５日放置した。
【００３３】
（塗膜の評価試験）
【００３４】
塗膜硬度：ＪＩＳ Ｋ５４００に準拠。
【００３５】
耐食性：ＪＩＳ Ｋ５４００に準じて行い、塩水噴霧テスト１０日間後のセロハンテープ剥離幅（ｍｍ）で示した。
【００３６】
耐水性：ＪＩＳ Ｚ８７３６に準じて行い、塗膜の白度（Lａｂ値）を、ダブルビーム分光式色差計（商品名「ＳＺII−Σ８０ ＴＹＰＥIII」、日本電色工業（株）製）で測定した。白度（Lａｂ値）は小さいほど耐水性は良好であり、２７以上：塗膜の白化が大きい、２５〜２６：塗膜の白化が多数みられる、２４以下：塗膜の白化が少ないまたは殆どない、を基準に判断した。
【００３７】
【表１】
BACKGROUND OF THE INVENTION
The present invention relates to an aqueous vinyl-modified epoxy resin, a method for producing the same, and an aqueous coating agent containing the vinyl-modified epoxy resin.
[0002]
[Prior art]
Conventionally, coating films obtained with water-based paints were considered to have poor corrosion resistance, but as an improvement in such corrosion resistance, vinyl-modified epoxy esters obtained by polymerizing vinyl monomers in the presence of fatty acid-modified epoxy esters Was developed. Since the vinyl-modified epoxy ester uses an epoxy resin as a component, it has high corrosion resistance, can be dried at room temperature with a fatty acid ester component, and can be made aqueous by selecting a vinyl monomer component. .
[0003]
However, as the field of application of water-based paints expands, the required performance for the coating film also increases, and a further increase in corrosion resistance and water resistance and high initial coating film hardness are required. For example, the conventional vinyl-modified epoxy ester has a low initial coating film hardness, and the coating film hardness gradually increases due to oxidative polymerization of the fatty acid component in the resin, and it takes several days to reach the target hardness. The initial damage was a problem. In addition, in the conventionally known vinyl-modified epoxy ester, a phenomenon that a black coating film prepared from the resin is whitened when immersed (hereinafter referred to as water whitening resistance) has also been a problem. Such water-whitening is improved by increasing the ratio of the fatty acid component in the vinyl-modified epoxy ester, but on the other hand, the coating film hardness and corrosion resistance are likely to decrease.
[0004]
[Problems to be solved by the invention]
The present invention provides an aqueous vinyl-modified epoxy resin aqueous material that has no deterioration in corrosion resistance, has a high initial coating film hardness, and is less susceptible to water whitening in a black coating film, and an aqueous coating agent comprising the aqueous vinyl-modified epoxy resin material. The purpose is to provide.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventor has produced a reaction product obtained by polymerizing a specific vinyl monomer in the presence of a polymerizable unsaturated group-containing modified epoxy resin that does not use fatty acids. The present inventors have found that a water-dispersed salt or aqueous solution of a product can solve the above-mentioned problems, and have completed the present invention.
[0006]
That is, the present invention relates to a polymerizable unsaturated group-containing modified epoxy resin (1) obtained by reacting a bisphenol type epoxy resin (1a), a glycidyl group-containing vinyl monomer (1b) and an amine (1c), and a carboxyl group-containing vinyl. An aqueous vinyl-modified epoxy resin, wherein the copolymer (A) obtained by copolymerizing the monomer (2) is neutralized with a basic compound and dispersed or dissolved in water; The present invention relates to a method for producing an aqueous material; and an aqueous coating comprising the aqueous material.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The copolymer (A) used in the present invention is a polymerizable unsaturated group-containing modified epoxy resin (1) obtained by reacting a bisphenol type epoxy resin (1a), a glycidyl group-containing vinyl monomer (1b), and an amine (1c) ( 1) and a carboxyl group-containing vinyl monomer (2) are copolymerized. In addition to the components (1a), (1b), (1c) and (2), the copolymer (A) can react with the component (1d) capable of reacting with the monomer, if necessary. Another vinyl monomer (3) that can be copolymerized with (2) can be an additional component.
[0008]
As described above, the polymerizable unsaturated group-containing modified epoxy resin (1) includes the bisphenol-type epoxy resin (1a), the glycidyl group-containing polymerizable vinyl monomer (1b), the amines (1c), and a component that can be reacted as necessary. It is a reaction product consisting of each constituent component consisting of (1d). That is, the epoxy group in the bisphenol-type epoxy resin (1a) is opened by the amines (1c), and at the same time, the amino group is introduced into the epoxy resin (1a), so that the original of the unmodified epoxy resin (1a) is obtained. It is considered that the adhesion, which is the performance of the above, is further improved. In addition, since the glycidyl group-containing polymerizable vinyl monomer (1b) reacts with the epoxy group in the bisphenol type epoxy resin (1a) via the amines (1c), there is a polymerizable unsaturated group in the epoxy resin (1a). Introduced and imparts copolymerizability.
[0009]
As the bisphenol type epoxy resin (1a) used in the present invention, various known ones can be used, and examples thereof include reaction products of bisphenols and haloepoxides such as epichlorohydrin or β-methylepichlorohydrin. Examples of the bisphenols include reaction products of phenol or 2,6-dihalophenol with aldehydes or ketones such as formaldehyde, acetaldehyde, acetone, acetophenone, cyclohexanone, benzophenone, peroxides of dihydroxyphenyl sulfide, and hydroquinones. And glycidyl ethers of aliphatic polyhydric alcohols, glycidyl ethers of aliphatic polybasic acids, and the like. The said epoxy resin can also use any 1 type independently, and can also use 2 or more types together suitably. The epoxy equivalent of the bisphenol-type epoxy resin (1a) component is preferably 3000 or less in consideration of the molecular weight of the copolymer (A) to be obtained and workability during production. When the epoxy equivalent exceeds 3000, there is a disadvantage that the molecular weight of the obtained copolymer (A) is increased and gelation is likely to occur.
[0010]
As the glycidyl group-containing vinyl monomer (1b), any known compound containing a glycidyl group and a polymerizable vinyl group in the molecule can be used without particular limitation. Specific examples include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (meth) allyl glycidyl ether, and the like.
[0011]
As the amines (1c), various known amines can be used without particular limitation. For example, alkanolamines, aliphatic amines, aromatic amines, alicyclic amines, aromatic nucleus-substituted aliphatic amines and the like can be mentioned, and these can be used by appropriately selecting one kind or two or more kinds. Specific examples of the amines (1c) include alkanolamines such as diethanolamine, diisopropanolamine, di-2-hydroxybutylamine, N-methylethanolamine, N-ethylethanolamine, and N-benzylethanol. Examples include amines. Examples of the aliphatic amines include primary amines such as ethylamine, propylamine, butylamine, hexylamine, laurylamine, stearylamine, palmitylamine, oleylamine, and erucylamine, and diethylamine, dipropylamine, and dibutylamine. Secondary amines can be mentioned. Examples of aromatic amines include toluidines, xylidines, cumidine (isopropylaniline), hexylanilines, nonylanilines, dodecylanilines and the like. Examples of the alicyclic amines include cyclopentylamines, cyclohexylamines, and norbornylamines. Examples of the aromatic nucleus-substituted aliphatic amines include benzylamine and phenethylamine.
[0012]
Moreover, in the polymerizable unsaturated group-containing modified epoxy resin (1), a reactive compound (1d) can be used as an additional component as described above. By modifying (high molecular weight) the polymerizable unsaturated group-containing modified epoxy resin (1) with the above compound (1d), the dispersibility of the resulting aqueous resin in water can be adjusted, Workability can be further improved. Examples of the compound (1d) include monovalent to trivalent organic acids, monovalent to tetravalent alcohols, and isocyanate compounds. As the monovalent to trivalent organic acid, various known aliphatic, alicyclic or aromatic carboxylic acids can be used, and examples thereof include dimer acid and trimellitic acid. As the monovalent to tetravalent alcohol, various known alcohols such as aliphatic, alicyclic or aromatic can be used, and examples thereof include neopentyl glycol, trimethylolpropane and pentaerythritol. As the isocyanate compound, various known aromatic, aliphatic or alicyclic polyisocyanates can be used, such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and the like. It is done.
[0013]
The production method of the polymerizable unsaturated group-containing modified epoxy resin (1) is not particularly limited, and various known methods can be applied. For example, the following conditions can be adopted. The proportions of the glycidyl group-containing vinyl monomer (1b), amines (1c) and other reactive compounds (1d) used relative to the bisphenol-type epoxy resin (1a) are in the following ranges, respectively. That is, the equivalent amount of active hydrogen derived from the amino group of the amines (1c) is 90 to 100 equivalents based on the total amount of epoxy groups contained in the bisphenol-type epoxy resin (1a) and the glycidyl group-containing vinyl monomer (1b). It is preferable to use so that it may become about 110 equivalent. Moreover, it is preferable to use so that the epoxy equivalent of a glycidyl group containing vinyl monomer (1b) may be about 1-25 equivalent with respect to 100 equivalent of epoxy groups of a bisphenol-type epoxy resin (1a). When the epoxy equivalent of the glycidyl group-containing vinyl monomer (1b) is less than 1, the storage stability of the modified epoxy resin aqueous product of the present invention is lowered, and when it exceeds 25, the modified epoxy resin (1) is produced. Sometimes it tends to gel. Moreover, the other compound (1d) which can be reacted can be used as needed in the range which does not impair the effect of this invention.
[0014]
The polymerizable unsaturated group-containing modified epoxy resin (1) can be easily produced by heating each of the above components in the presence of the following organic solvent. The reaction temperature is usually about 60 to 200 ° C., but if the reaction temperature is too low, an unreacted epoxy group tends to remain, and preferably 80 ° C. or higher. On the other hand, if the reaction temperature is too high, the reaction product is easily gelled due to the ring-opening reaction between the epoxy group in the modified epoxy resin (1) and the hydroxyl group in the other component or the ring-opening reaction between the epoxy groups. Therefore, the temperature is preferably 150 ° C. or lower. Moreover, although reaction time is dependent on reaction temperature, it is good to set it as 3 to 10 hours on the said temperature conditions.
[0015]
As the organic solvent, it is desirable to use a hydrophilic solvent from the viewpoint of making the vinyl-modified epoxy resin finally obtained aqueous, specifically, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n. -Butyl ether, propylene glycol mono-t-butyl ether, methyl cellosolve, ethyl cellosolve, n-butyl cellosolve, t-butyl cellosolve, isopropyl alcohol, butyl alcohol and the like.
[0016]
The copolymer (A) used in the present invention comprises a polymerizable unsaturated group-containing modified epoxy resin (1) obtained as described above, a carboxyl group-containing vinyl monomer (2), and, if necessary, It is produced by copolymerizing the monomer (2) with another vinyl monomer (3) that can be copolymerized. The copolymer (A) in the present invention corresponds to a vinyl graft-amine modified epoxy resin. In the present invention, the polymerizable unsaturated group of the polymerizable unsaturated group-containing modified epoxy resin (1) is copolymerized with the carboxyl group-containing vinyl monomer (2) and, if necessary, another monomer (3). It is important to produce a graft body. By such grafting, it is possible to obtain a copolymer (A) that can be stably dispersed or dissolved in water while maintaining high corrosion resistance and adhesion, which are the original properties of the epoxy resin (1a).
[0017]
Examples of the carboxyl group-containing vinyl monomer (2) copolymerized with the polymerizable unsaturated group-containing modified epoxy resin (1) include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. And carboxyl group-containing vinyl monomers. Examples of the other vinyl monomer (3) that is an optional component copolymerizable with the carboxyl group-containing vinyl monomer (2) include methyl acrylate, ethyl acrylate, n-propyl acrylate, and acrylic acid. acrylic esters such as n-butyl, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, Methacrylic acid esters such as tert-butyl methacrylate and 2-ethylhexyl methacrylate; Styrene vinyl monomers such as styrene, vinyltoluene and α-methylstyrene; Others, vinyl acetate, β-hydroxyethyl acrylate, acrylic acid Glycidyl, glycidyl methacrylate, acrylic Amide, N, N-diethyl methacrylamide, acrylonitrile, methacrylonitrile and the like. These vinyl monomers (2) and (3) can be used alone or in combination of two or more.
[0018]
The carboxyl group-containing vinyl monomer (2) is essential for facilitating aqueous formation (stable water dispersion or dissolution) of the resulting vinyl-modified epoxy resin. Therefore, the amount of the carboxyl group-containing vinyl monomer (2) used is determined from the viewpoint of making the resulting vinyl-modified epoxy resin aqueous, and the solid content acid value of the vinyl-modified epoxy resin is 15 or more, more preferably 20 or more. It is preferable to adjust so that. On the other hand, in order to impart good water resistance and corrosion resistance to the vinyl-modified epoxy resin, it is preferable to adjust the amount used so that the solid content acid value of the vinyl-modified epoxy resin is 45 or less, and further 40 or less. In addition, even when other vinyl monomer (3), which is an optional component, is used in combination with the carboxyl group-containing vinyl monomer (2), from the same viewpoint as described above, the amount of both these components can be determined, It is preferable to adjust the solid content acid value of the resulting vinyl-modified epoxy resin as appropriate within the same range as described above.
[0019]
In the copolymerization of the polymerizable unsaturated group-containing modified epoxy resin (1) with the carboxyl group-containing vinyl monomer (2) and, if necessary, other vinyl monomers (3), the polymerization initiator used is particularly There is no restriction | limiting, A well-known various organic peroxide and an azo compound can be used. Examples include benzoyl peroxide, tert-butyl peroctoate, 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), and the like.
[0020]
The copolymerization is not limited to a polymerization mode, but a solution polymerization method is preferable. For example, the polymerization can be performed at a reaction temperature of about 60 to 150 ° C. in the presence of the polymerization initiator as described above. About the organic solvent, the thing similar to what was used in manufacture of the said polymerizable unsaturated group containing modified epoxy resin (1) can be used. Polymerizable unsaturated group-containing modified epoxy resin (1), carboxyl group-containing vinyl monomer (2), and other vinyl monomer (3) in use weight ratio ((1) / [(2) + (3 )]) Can be appropriately determined in view of the solid content acid value of the copolymer (A) obtained as described above, but is usually within the range of 99/1 to 80/20. If the amount of the monomer used is less than the lower limit, water dispersibility or water solubility becomes unstable and precipitation occurs in the product. On the other hand, if the vinyl monomer exceeds the upper limit, adhesion and corrosion resistance, which are the original characteristics of the vinyl-modified epoxy resin, are likely to be lowered.
[0021]
The copolymer (A) thus obtained is neutralized with a basic compound and dissolved or dispersed in water to give the intended aqueous vinyl-modified epoxy resin. That is, it is preferable to neutralize all or part of the carboxyl groups derived from the vinyl monomer (2) in the copolymer (A) so that the pH is about 7 to 10. As the basic compound which is a neutralizing agent, amines such as ammonia, triethylamine and dimethylethanolamine, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, etc. can be used. In view of volatility, ammonia and amines are preferable.
[0022]
The aqueous vinyl-modified epoxy resin of the present invention can be used in various applications as an aqueous coating agent (for example, a coating agent such as a paint or an adhesive) for various materials such as wood, paper, fiber, plastic, ceramic, iron, and non-ferrous metal. . In application to various applications, it can be diluted with water and used as it is, and if necessary, pigments, plasticizers, solvents, colorants, antifoaming agents, etc. can be added, or other water-soluble or water-dispersible resins Can also be blended.
[0023]
【The invention's effect】
The vinyl-modified epoxy resin of the present invention has a high degree of corrosion resistance comparable to conventional epoxy ester resins, has a high initial hardness of the coating film, and is excellent in water resistance (water whitening in a black coating film, etc.) It can be used as various aqueous coating materials such as paints.
[0024]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.
[0025]
Example 1
In a reaction apparatus equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas introduction tube, tert-butyl cellosolve 120 g, bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-014, epoxy equivalent 950) and glycidyl methacrylate After adding 5.6 g and dissolving at 100 ° C. under a nitrogen stream, 18.4 g of octylamine and 17.7 g of di-2-ethylhexylamine are added and reacted for 5 hours to obtain a polymerizable unsaturated group-containing modified epoxy resin. It was. Then, a mixture of 13 g of acrylic acid, 40 g of tert-butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour and kept for 4 hours. After cooling to 80 ° C., 18 g of triethylamine and 480 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 650 mPa · s, a pH of 9.7, and a solid content acid value of 28.
[0026]
Example 2
120 g of tert-butyl cellosolve, 300 g of bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-014, epoxy equivalent 950) and 5.6 g of glycidyl methacrylate were added to the same reactor as in Example 1, and the flow was 100 under nitrogen flow. After dissolving at 0 ° C., 18.4 g of octylamine and 17.7 g of di-2-ethylhexylamine were added and reacted for 5 hours to obtain a polymerizable unsaturated group-containing modified epoxy resin. Next, a mixture of 15 g of acrylic acid, 12 g of styrene, 12 g of butyl acrylate, 40 g of tert-butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour and 4 hours. Keep warm. After cooling to 80 ° C., 21 g of triethylamine and 540 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 450 mPa · s, a pH of 9.7, and a solid content acid value of 30.
[0027]
Example 3
After adding 120 g of tert-butyl cellosolve, 300 g of bisphenol A type epoxy resin (epototo YD-014) and 7.5 g of glycidyl methacrylate to the same reactor as in Example 1, the mixture was dissolved at 100 ° C. under a nitrogen stream, and then octylamine 18. 9 g, 9.0 g of monoethanolamine, and 23.6 g of di-2-ethylhexylamine were reacted for 5 hours. Further, 8.0 g of hexamethylene diisocyanate was added and reacted for 5 hours to obtain a polymerizable unsaturated group-containing modified epoxy resin. Obtained. Next, 15 g of acrylic acid, 6 g of styrene, 6 g of butyl acrylate, 40 g of tert-butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate were added dropwise to the reaction system over 1 hour, and the temperature was kept for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 560 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 700 mPa · s, a pH of 9.7, and a solid content acid value of 30.
[0028]
Example 4
120 g of tert-butyl cellosolve, 300 g of bisphenol A type epoxy resin (Epototo YD-014) and 5.6 g of glycidyl methacrylate were added to the same reactor as in Example 1 and dissolved at 100 ° C. in a nitrogen stream. 4 g and 17.7 g of di-2-ethylhexylamine were added and reacted for 5 hours to obtain a polymerizable unsaturated group-containing modified epoxy resin. Then, a mixture of 18 g of acrylic acid, 45 g of styrene, 45 g of butyl acrylate, 50 g of tert-butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour and 4 hours. Keep warm. After cooling to 80 ° C., 21 g of triethylamine and 660 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 350 mPa · s, a pH of 9.7, and a solid content acid value of 31.
[0029]
Comparative Example 1
120 g of t-butyl cellosolve and 300 g of bisphenol A type epoxy resin (Epototo YD-014) were added to the same reaction apparatus as in Example 1, and dissolved at 100 ° C. under a nitrogen stream. Then, 16.3 g of octylamine and di-2- 15.2 g of ethylhexylamine was added and reacted for 5 hours to obtain a modified epoxy resin. Next, a mixture of 15 g of acrylic acid, 12 g of styrene, 12 g of butyl acrylate, 40 g of tert-butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour and 4 hours. Keep warm. After cooling to 80 ° C., 21 g of triethylamine and 540 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 250 mPa · s, a pH of 9.7, and a solid content acid value of 32. The aqueous dispersion formed a precipitate after 1 day.
[0030]
Comparative Example 2
In a 1 liter glass flask equipped with a stirrer, thermometer, reflux dehydrator and nitrogen gas inlet tube, 200 g of bisphenol A type epoxy resin (Epototo YD-014), 96 g of soybean oil fatty acid and 0.15 g of sodium bicarbonate were added. Then, heating was performed at 220 ° C. while blowing nitrogen gas, and addition and condensation were performed until the acid value became 1 or less to obtain a fatty acid-modified epoxy ester. 250 g of the obtained fatty acid-modified epoxy ester and 50 g of tert-butyl cellosolve were put in the same reaction apparatus, and heated and stirred at 130 ° C. Subsequently, a mixture of 18 g of styrene, 14 g of acrylic acid, 3 g of tert-peroxybenzoate and 80 g of tert-butyl cellosolve was dropped into the reaction system over 1 hour, and the temperature was further kept for 4 hours. After cooling to 80 ° C., 19 g of triethylamine and 400 g of water were sequentially added and mixed to obtain an aqueous dispersion of vinyl-modified epoxy ester having a non-volatile content of 34.8%, a viscosity of 300 mPa · s, a pH of 9.7, and a solid content acid value of 35. Obtained.
[0031]
Water-based paints were prepared from the vinyl-modified epoxy resin aqueous materials obtained in Examples and Comparative Examples with the following composition, and the performance of the coating films obtained from the paints was evaluated by the following methods. The evaluation results are shown in Table 1.
[0032]
(Preparation of water-based paint)
A mixture of 44.6 g of an aqueous vinyl-modified epoxy resin, 1.8 g of carbon black, 5.6 g of zinc phosphate, 23.8 g of calcium carbonate, 1.8 g of deionized water, and 80 g of glass beads, was mixed for 1 hour 30 with a paint shaker. Kneaded. Thereafter, 23 g of an aqueous dispersion of vinyl-modified epoxy resin was mixed, and then the glass beads were removed to obtain an aqueous paint. In addition, when any vinyl-modified epoxy resin aqueous material is used, the PWC (pigment weight concentration) of the aqueous paint is 57%, and the paint concentration is 53.2% (solvent amount 10.2%). did. The obtained water-based paint was applied to a degreased dull steel plate (SPCC-SD, 0.8 × 70 × 150 mm) with a bar coater so that the film thickness after drying was 20 μm, and forced drying (80 ° C. × 20 minutes), and left at room temperature (20 ° C., 60% RH) for 5 days.
[0033]
(Evaluation test of coating film)
[0034]
Coating hardness: Conforms to JIS K5400.
[0035]
Corrosion resistance: Measured according to JIS K5400, and indicated by cellophane tape peel width (mm) after 10 days of salt spray test.
[0036]
Water resistance: Performed according to JIS Z8736, and the whiteness (Lab value) of the coating film was measured with a double beam spectroscopic color difference meter (trade name “SZII-Σ80 TYPE III”, manufactured by Nippon Denshoku Industries Co., Ltd.). The smaller the whiteness (Lab value), the better the water resistance, 27 or more: large whitening of the coating film, 25 to 26: many whitenings of the coating film are observed, 24 or less: little or no whitening of the coating film Judged on the basis of no.
[0037]
[Table 1]
Claims (7)
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| KR101238980B1 (en) * | 2005-06-30 | 2013-03-04 | 아라까와 가가꾸 고교 가부시끼가이샤 | Aqueous liquid containing vinyl-modified epoxy resin, process for producing the same, and water-based coating material |
| JP5099320B2 (en) * | 2007-07-23 | 2012-12-19 | 荒川化学工業株式会社 | Aqueous vinyl-modified epoxy resin, production method thereof, and aqueous coating agent |
| WO2009066588A1 (en) | 2007-11-19 | 2009-05-28 | Arakawa Chemical Industries, Ltd. | Aqueous resin composition for coating, and aqueous coating |
| WO2016047458A1 (en) * | 2014-09-22 | 2016-03-31 | 荒川化学工業株式会社 | Modified epoxy resin for coating material, and single component lacquer type coating material |
| JP7081522B2 (en) * | 2018-02-13 | 2022-06-07 | 荒川化学工業株式会社 | Vinyl-modified epoxy resin composition, water-based coating agent |
| CN114958134A (en) * | 2022-07-19 | 2022-08-30 | 石家庄市鱼莎电力物资工程有限公司 | Water-based epoxy moisture-curing acid-and-alkali-resistant coating and preparation method thereof |
| JP7188634B1 (en) * | 2022-09-01 | 2022-12-13 | 荒川化学工業株式会社 | Modified epoxy resin composition, aqueous coating agent |
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