JP7364598B2 - 電磁鋼帯または電磁鋼板、該電磁鋼帯または電磁鋼板の製造方法、およびそれから構成される金属薄板積層体 - Google Patents
電磁鋼帯または電磁鋼板、該電磁鋼帯または電磁鋼板の製造方法、およびそれから構成される金属薄板積層体 Download PDFInfo
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Description
従来技術から、電磁鋼帯または電磁鋼板の表面を接着材料でコーティングし、それから切断した板金部品を材料結合により接着させて金属薄板積層体を形成するための多数の方法が公知である。例えば、電磁鋼帯ないしは電磁鋼板を、熱硬化性溶融接着ワニス、つまり焼付ワニスとも呼ばれる、溶融接着材料を含む反応性接着材料系でコーティングする(国際公開第2014/089593号)。乾燥後、つまり熱硬化性溶融接着ワニス層から溶媒を除去した後に、そのようにコーティングされた電磁鋼帯ないしは電磁鋼板から切断した板金部品を互いに積み重ね、いわゆる焼付プロセスによりまず接着させ、次いで硬化させる、つまり、圧力、温度および時間のパラメータにより互いに材料結合により結合させて積層体を形成する。卓越した磁気特性を有する高硬度の金属薄板積層体を得るためには、溶融接着ワニスの接着性ないしは接着状態を、詳細には電磁鋼帯または電磁鋼板に塗布する前から乾燥まで、ないしは最終硬化まで、つまり焼付プロセスまで、できるだけ一定に調整するないしは安定に維持することが重要である。プロセス工学的に問題があると判明したのは、特に材料結合による結合である。なぜなら、その際、焼付プロセスの間の焼付ワニスの流出を防止することが非常に重要であるためである。
したがって、本発明は、冒頭で述べた従来技術を起点に、その平坦面のうちの一方の上に設けられた、焼付プロセスの間に高まった溶融粘度を有する少なくとも1つの熱硬化性水性溶融接着ワニス層を有する電磁鋼帯または電磁鋼板を提供することを課題とした。
予備架橋剤の重量%=[エポキシ樹脂またはエポキシ樹脂の混合物の重量%/エポキシ樹脂またはエポキシ樹脂の混合物の平均M]×[予備架橋剤の平均M/(X×予備架橋剤分子の平均アミノ基数)]
[式中、Xは、1.6~28.9、特に2.1~19.4、特に2.9~7.2の数を表し、Mは、モル質量を表す]。
1500~2000g/molの平均モル質量を有するエポキシ樹脂またはエポキシ樹脂の混合物35~55重量%、特に40~50重量%、および
予備架橋剤としての、350~550g/molの平均モル質量を有するトリアミン0.1~2重量%、特に0.2~1.0重量%
を有する場合に達成され得る。
1500~2000g/molの平均モル質量を有するエポキシ樹脂またはエポキシ樹脂の混合物35~55重量%、特に40~50重量%、および
予備架橋剤としての350~550g/molの平均モル質量を有するトリアミン0.1~2重量%、特に0.2~1.0重量%、
シアナミドベースの潜在性硬化剤、特にジシアンジアミド2~10重量%、特に3~8重量%、および
残部としての水、および補助溶媒、好ましくは補助溶媒としての1-メトキシプロパノールを特に4~20重量%有する場合に達成され得る。
1500~2000g/molの平均モル質量を有するエポキシ樹脂またはエポキシ樹脂の混合物75~92.8重量%、特に80~90重量%、
硬化剤、特にジシアナミド4~24.8重量%、特に7~12重量%、
予備架橋剤としての350~550g/molの平均モル質量を有するトリアミン0.2~4重量%、特に0.4~2重量%
を有する乾燥した熱硬化性溶融接着ワニス層が特に傑出し得る。
以下に、一変形実施形態をもとに本発明を例示的に記載する。
本発明により改善された、最適な予備架橋を達成するための関係によって、特に溶融接着ワニス層の保存安定性、取扱い性、および流出防止性(Ausfliesssicherheit)の特に有利なバランスが可能となり得る。Xの値が大きいほど、エポキシ樹脂またはエポキシ樹脂の混合物に対する予備架橋剤の量が少なくなる。Xの値が小さすぎる、それゆえ相対的に予備架橋剤の重量%が大きすぎると、溶融接着ワニスが使用前にすでにゲル化することがあり、それにより溶融接着ワニスの塗布がすでに困難になるであろう危険性ゆえ、より不都合な保存安定性をもたらしかねない。Xの値が大きすぎる、それゆえ相対的に予備架橋剤の重量%が小さすぎると、特に予備架橋度が過度に低くなり、溶融接着ワニスが過度に低粘度になり、それゆえもはや流出安定性でなくなることにつながりかねない。
2000g/molの平均モル質量を有するエポキシ樹脂50グラム、
潜在性硬化剤としてのジシアンジアミド5.0グラム、
予備架橋剤としての440g/molの平均モル質量を有するトリアミン、つまり末端エーテル基の第二級炭素原子に結合している3つの第一級アミノ基を有する以下の構造式
補助溶媒としての1-メトキシプロパノール10グラム、および
残部としての水
を有する熱硬化性水性溶融接着ワニス層で電磁鋼帯または電磁鋼板がコーティングされている。
予備架橋剤の重量%=[エポキシ樹脂またはエポキシ樹脂の混合物の重量%/エポキシ樹脂またはエポキシ樹脂の混合物の平均M]×[予備架橋剤の平均M/(X×予備架橋剤分子の平均アミノ基数)]
[式中、Mは、モル質量を表す。Xについては、実施例1では、値3.67が得られ、この値も同様に、特に好ましく特許請求される範囲2.9~7.2内にある]を満たす。
試料1の熱硬化性溶融接着ワニス層の組成は、従来の市販入手可能な焼付ワニスに相当する。
試料2の熱硬化性溶融接着ワニス層の組成は、本発明による実施例1(試料3)の組成に相当するものの、予備架橋剤が添加されていない。
熱硬化性溶融接着ワニス層の組成は、本発明による実施例1の組成に相当する。これを、5μmの層厚で、ケイ素合金(Si約3%)電磁鋼帯上にローラ塗布し、220℃の帯温度(PMT-Peak Metal Temperature)で乾燥させた。
Claims (22)
- 電磁鋼帯または電磁鋼板であって、その平坦面のうちの一方の上に設けられた、エポキシ樹脂またはエポキシ樹脂混合物、少なくとも1つの硬化剤、および残部としての水を有する少なくとも1つの熱硬化性水性溶融接着ワニス層を有する電磁鋼帯または電磁鋼板において、前記熱硬化性水性溶融接着ワニス層が、さらに前記エポキシ樹脂またはエポキシ樹脂の混合物と結合する予備架橋剤を有し、前記予備架橋剤が、3つのアミノ基を有する有機アミン、すなわち有機トリアミン、または該有機アミンの混合物であり、
前記熱硬化性水性溶融接着ワニス層における予備架橋剤およびエポキシ樹脂またはエポキシ樹脂混合物の重量%が、以下の関係:
予備架橋剤の重量%=[エポキシ樹脂またはエポキシ樹脂の混合物の重量%/エポキシ樹脂またはエポキシ樹脂の混合物の平均M]×[予備架橋剤の平均M/(X×予備架橋剤分子の平均アミノ基数)]
[式中、Xは、1.6~28.9の数を表し、Mは、モル質量を表す]
を満たし、
前記エポキシ樹脂またはエポキシ樹脂の混合物が、ビスフェノールAベースを有し、
前記熱硬化性水性溶融接着ワニス層が、1500~2000g/molの平均モル質量を有するエポキシ樹脂またはエポキシ樹脂の混合物35~55重量%、予備架橋剤としての350~550g/molの平均モル質量を有するトリアミン0.1~2重量%、およびシアナミドベースの潜在性硬化剤を2~10重量%有することを特徴とする、電磁鋼帯または電磁鋼板。 - Xは、2.1~19.4の数を表す、請求項1記載の電磁鋼帯または電磁鋼板。
- Xは、2.9~7.2の数を表す、請求項1記載の電磁鋼帯または電磁鋼板。
- 前記予備架橋剤の前記3つのアミノ基が、それぞれ第一級アミノ基であることを特徴とする、請求項1から3までのいずれか1項記載の電磁鋼帯または電磁鋼板。
- 前記予備架橋剤が、ポリエーテルトリアミンであることを特徴とする、請求項1から4までのいずれか1項記載の電磁鋼帯または電磁鋼板。
- 前記予備架橋剤が、ポリオキシプロピレントリアミンであることを特徴とする、請求項1から4までのいずれか1項記載の電磁鋼帯または電磁鋼板。
- 前記ポリエーテルトリアミンの1つのアミノ基が、末端エーテル基の第二級炭素原子に結合していることを特徴とする、請求項5または6記載の電磁鋼帯または電磁鋼板。
- 前記ポリエーテルトリアミンのすべてのアミノ基が、末端エーテル基の第二級炭素原子に結合していることを特徴とする、請求項5または6記載の電磁鋼帯または電磁鋼板。
- 熱硬化性水性溶融接着ワニス層が、シアナミドベースの常温潜在性硬化剤を有することを特徴とする、請求項1から8までのいずれか1項記載の電磁鋼帯または電磁鋼板。
- 熱硬化性水性溶融接着ワニス層が、ジシアンジアミドからなる常温潜在性硬化剤を有することを特徴とする、請求項1から8までのいずれか1項記載の電磁鋼帯または電磁鋼板。
- 前記熱硬化性水性溶融接着ワニス層が、
1500~2000g/molの平均モル質量を有するエポキシ樹脂またはエポキシ樹脂の混合物40~50重量%、および/または
予備架橋剤としての350~550g/molの平均モル質量を有するトリアミン0.2~1.0重量%
を有することを特徴とする、請求項1から10までのいずれか1項記載の電磁鋼帯または電磁鋼板。 - 前記熱硬化性水性溶融接着ワニス層が、
ジシアンジアミドを3~8重量%有することを特徴とする、請求項1から11までのいずれか1項記載の電磁鋼帯または電磁鋼板。 - 前記熱硬化性水性溶融接着ワニス層が、補助溶媒を有することを特徴とする、請求項1から12までのいずれか1項記載の電磁鋼帯または電磁鋼板。
- 前記熱硬化性水性溶融接着ワニス層が、補助溶媒を4~20重量%有することを特徴とする、請求項1から12までのいずれか1項記載の電磁鋼帯または電磁鋼板。
- 前記熱硬化性水性溶融接着ワニス層が、補助溶媒として1-メトキシプロパノールを有することを特徴とする、請求項14記載の電磁鋼帯または電磁鋼板。
- 前記電磁鋼帯または電磁鋼板の熱硬化性溶融接着ワニス層が乾燥している、請求項1から15までのいずれか1項記載の電磁鋼帯または電磁鋼板。
- 乾燥した熱硬化性溶融接着ワニス層が、
1500~2000g/molの平均モル質量を有するエポキシ樹脂またはエポキシ樹脂の混合物75~92.8重量%、
硬化剤4~24.8重量%、
予備架橋剤としての350~550g/molの平均モル質量を有するトリアミン0.2~4重量%
を有することを特徴とする、請求項1から10までのいずれか1項記載の電磁鋼帯または電磁鋼板。 - 前記乾燥した熱硬化性溶融接着ワニス層が、
1500~2000g/molの平均モル質量を有するエポキシ樹脂またはエポキシ樹脂の混合物80~90重量%、および/または
ジシアナミド7~12重量%、および/または
予備架橋剤としての350~550g/molの平均モル質量を有するトリアミン0.4~2重量%
を有することを特徴とする、請求項17記載の電磁鋼帯または電磁鋼板。 - 熱硬化性水性溶融接着ワニスの、電磁鋼帯または電磁鋼板の少なくとも1つの平坦面への塗布によって、請求項1から18までのいずれか1項記載の電磁鋼帯または電磁鋼板を製造する方法。
- 熱硬化性水性溶融接着ワニスの、電磁鋼帯または電磁鋼板の少なくとも1つの平坦面へのローラ塗布または吹付けによって、請求項1から18までのいずれか1項記載の電磁鋼帯または電磁鋼板を製造する方法。
- 溶融接着ワニス層の乾燥、
電磁鋼帯または電磁鋼板からの板金部品の切断、
前記板金部品の積み重ねによる、金属薄板積層体の形成、
前記金属薄板積層体の、前記溶融接着ワニス層の熱活性化による、接着
を含む、請求項19または20記載の、電磁鋼帯または電磁鋼板を用いた金属薄板積層体の製造方法。 - 180~280℃の帯温度における溶融接着ワニス層の乾燥、および/または
前記金属薄板積層体の、100~250℃における前記溶融接着ワニス層の熱活性化による、接着
を含む、請求項21記載の、電磁鋼帯または電磁鋼板を用いた金属薄板積層体の製造方法。
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