JP4183463B2 - Amorphous alloy ribbon laminate and method for producing the same - Google Patents
Amorphous alloy ribbon laminate and method for producing the same Download PDFInfo
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Description
【０００１】
【産業上の利用分野】
本発明は、樹脂を媒体として非晶質合金薄帯が積層接着された非晶質合金薄帯積層体に関し、より詳細には、磁気応用部品として優れた磁気性能と強度を併せ持つ非晶質合金薄帯積層体に関する。
【０００２】
【従来の技術】
非晶質合金薄帯は、各種金属を原材料に溶融状態から急激に冷却することで製造される非結晶の固体であり、通常は厚さ約０．０１〜０．１ミリメートル程度の薄帯である。これら非晶質合金薄帯においては、原子は配列に規則性がないランダム構造であり、軟磁性材料として優れた特性を有している。特にＣｏ元素を含むＣｏ系非晶質合金薄帯は、高い比透磁率と低いコア損失を併せ持った材料であり、種々の磁気応用部品、例えばインダクタンス、各種コイル、各種トランス、ノイズフィルター、磁気センサー、磁気ヘッド、アンテナ、電波吸収体、モーター、各種コア、配線基板など、幅広い分野において用いられることが期待されている。
【０００３】
非晶質合金薄帯は、その優れた磁気特性を発現させるために、予め所定の焼鈍熱処理を施す方法が一般に用いられている。焼鈍熱処理の条件は発現させたい磁気特性や非晶質合金の種類によって異なるが、概ね不活性雰囲気下において温度３００〜５００℃程度、時間０．１〜１００時間程度の高温長時間で行われることが一般的である。ところが焼鈍熱処理によって優れた磁気特性を発現する反面、極めて脆弱な薄帯となり、物理的に取り扱いにくくなる問題を抱えている。
【０００４】
この問題に対処する方法として、ポリイミド樹脂などの焼鈍温度に耐える耐熱性高分子化合物を接着剤として用い、非晶質合金薄帯を積層接着する方法が開示されている（特許文献１）。この方法によれば、焼鈍と同時に耐熱性樹脂による接着積層ができるため、脆弱な薄帯を取り扱う問題を解決できる。しかし、耐熱性樹脂を用いることによって非晶質合金薄帯に不要な応力が生じ、樹脂を用いない場合に比べて、磁気特性が低減する問題が新たに生じる。すなわち、非晶質合金薄帯が本来有する優れた磁気特性を十分に発揮させることができない。また、実質的にＦｅ系非晶質合金薄帯を巻回によって積層させたコアについて検討されているに留まっており、Ｃｏ系非晶質合金薄帯に関して、その磁気特性を十分に発現させるための技術は、何ら開示されていない。
【０００５】
以上のように、非晶質合金薄帯が本来有する優れた磁気特性を持ちながら、機械的強度を併せ持つ材料は未だ見出されていないのが実状であり、その開発が望まれている。
【０００６】
【特許文献１】
特開昭５８−１７５６５４
【０００７】
【本発明が解決しようとする課題】
本発明の目的は、上記従来技術の問題点に鑑み、Ｃｏ系非晶質合金薄帯が本来有する優れた磁気特性と機械的強度を併せ持つ非晶質合金薄帯積層体、およびその製造方法を提供することにある。
【０００８】
【課題を解決するための手段】
本発明者らは、前記課題を解決するために鋭意検討を重ねた結果、樹脂を媒体として非晶質合金薄帯が積層接着された非晶質合金薄帯積層体において、非晶質合金薄帯としてＣｏ系非晶質合金薄帯を用い、特定の条件において積層接着および焼鈍を同時に行うことにより、また特定の条件において積層接着を行い、次いで特定の条件において焼鈍を行うことにより、Ｃｏ系非晶質合金薄帯が本来有する優れた磁気特性と機械的強度を併せ持つ非晶質合金薄帯積層体となることを見出し、本発明を完成した。
【０００９】
すなわち、本発明は、以下の［１］〜［６］に記載した事項により特定される。
【００１０】
[１] 樹脂を媒体として非晶質合金薄帯が積層接着された非晶質合金薄帯積層体において、該非晶質合金の元素組成が［Ｃｏ１−ｃ・Ｆｅｃ］１００−ａ−ｂ・Ｘａ・Ｙｂ（但し、ＸはＳｉ、Ｂ、Ｃ、Ｇｅから選ばれる少なくとも一種類以上の元素を表し、ＹはＺｒ、Ｎｂ、Ｔｉ、Ｈｆ、Ｔａ、Ｗ、Ｃｒ、Ｍｏ、Ｖ、Ｎｉ、Ｐ、Ａｌ、Ｐｔ、Ｒｈ、Ｒｕ、Ｓｎ、Ｓｂ、Ｃｕ、Ｍｎまたは希土類元素から選ばれる少なくとも一種類以上の元素を表す。またａ、ｂ、ｃはそれぞれ、１０＜ａ≦３５、０≦ｂ≦３０、０≦ｃ≦０．３で表される数である。）で表され、閉磁路系で測定される周波数１００ｋＨｚにおける該非晶質合金薄帯積層体の比透磁率μが１２、０００以上およびコア損失Ｐｃが１２Ｗ／ｋｇ以下であり、該非晶質合金薄帯積層体の引っ張り強度が３０ＭＰａ以上であることを特徴とする非晶質合金薄帯積層体。
【００１１】
[２] 元素組成が［Ｃｏ１−ｃ・Ｆｅｃ］１００−ａ−ｂ・Ｘａ・Ｙｂ（但し、ＸはＳｉ、Ｂ、Ｃ、Ｇｅから選ばれる少なくとも一種類以上の元素を表し、ＹはＺｒ、Ｎｂ、Ｔｉ、Ｈｆ、Ｔａ、Ｗ、Ｃｒ、Ｍｏ、Ｖ、Ｎｉ、Ｐ、Ａｌ、Ｐｔ、Ｒｈ、Ｒｕ、Ｓｎ、Ｓｂ、Ｃｕ、Ｍｎまたは希土類元素から選ばれる少なくとも一種類以上の元素を表す。またａ、ｂ、ｃはそれぞれ、１０＜ａ≦３５、０≦ｂ≦３０、０≦ｃ≦０．３で表される数である。）で表される非晶質合金薄帯の片面または両面に樹脂層を形成させた複合薄帯を重ね合わせ、圧力０．０１〜１００ＭＰａ、温度３５０〜４８０℃、時間１〜３００分の条件で積層接着および焼鈍を同時に行うことを特徴とする、樹脂を媒体として非晶質合金薄帯が積層接着された非晶質合金薄帯積層体の製造方法。
【００１２】
[３] 元素組成が［Ｃｏ１−ｃ・Ｆｅｃ］１００−ａ−ｂ・Ｘａ・Ｙｂ（但し、ＸはＳｉ、Ｂ、Ｃ、Ｇｅから選ばれる少なくとも一種類以上の元素を表し、ＹはＺｒ、Ｎｂ、Ｔｉ、Ｈｆ、Ｔａ、Ｗ、Ｃｒ、Ｍｏ、Ｖ、Ｎｉ、Ｐ、Ａｌ、Ｐｔ、Ｒｈ、Ｒｕ、Ｓｎ、Ｓｂ、Ｃｕ、Ｍｎまたは希土類元素から選ばれる少なくとも一種類以上の元素を表す。またａ、ｂ、ｃはそれぞれ、１０＜ａ≦３５、０≦ｂ≦３０、０≦ｃ≦０．３で表される数である。）で表される非晶質合金薄帯の片面または両面に樹脂層を形成させた複合薄帯を重ね合わせ、圧力０．０１〜５００ＭＰａ、温度２００〜３５０℃、時間１〜３００分の条件で積層接着を行い、次いで圧力０〜１００ＭＰａ、温度３５０〜４８０℃、時間１〜３００分の条件で焼鈍を行うことを特徴とする、樹脂を媒体として非晶質合金薄帯が積層接着された非晶質合金薄帯積層体の製造方法。
【００１３】
［４］ ［２］または［３］記載の方法で製造される樹脂を媒体として非晶質合金薄帯が積層接着された非晶質合金薄帯積層体。
【００１４】
［５］ ［２］または［３］記載の方法で製造される請求項１記載の非晶質合金薄帯積層体。
【００１５】
［６］ ［１］、［４］または［５］記載の非晶質合金薄帯積層体を含んで構成される磁気応用部品。
【００１６】
【発明の実施の形態】
本発明の非晶質合金薄帯積層体は、樹脂を媒体として非晶質合金薄帯が積層接着された非晶質合金薄帯積層体である。
【００１７】
本発明において用いる非晶質合金薄帯は、その元素組成が［Ｃｏ１−ｃ・Ｆｅｃ］１００−ａ−ｂ・Ｘａ・Ｙｂで表されるものである。但し、ＸはＳｉ、Ｂ、Ｃ、Ｇｅから選ばれる少なくとも一種類以上の元素を表し、ＹはＺｒ、Ｎｂ、Ｔｉ、Ｈｆ、Ｔａ、Ｗ、Ｃｒ、Ｍｏ、Ｖ、Ｎｉ、Ｐ、Ａｌ、Ｐｔ、Ｒｈ、Ｒｕ、Ｓｎ、Ｓｂ、Ｃｕ、Ｍｎまたは希土類元素から選ばれる少なくとも一種類以上の元素を表す。またａ、ｂ、ｃはそれぞれ、１０＜ａ≦３５、０≦ｂ≦３０、０≦ｃ≦０．３で表される数である。元素Xは、非晶質合金薄帯を製造する上で、非晶質化のために結晶化速度を低減するために有効な元素である。ａが１０より小さい場合には非晶質化が低下して一部結晶質が混在する恐れがあり、またａが３５を超えると、非晶質構造は得られるものの合金薄帯の機械的強度が低下し、連続的な薄帯が得られなくなる恐れがある。従って、本発明において１０＜ａ≦３５であり、１２≦ａ≦３０であることがより好ましい。元素Ｙは、非晶質合金薄帯の耐食性に効果がある。この中で特に有効な元素は、Ｚｒ、Ｎｂ、Ｍｎ、Ｗ、Ｍｏ、Ｃｒ、Ｖ、Ｎｉ、Ｐ、Ａｌ、Ｐｔ、Ｒｕ、Ｒｈである。ｂが３０を越えると非晶質合金薄帯の機械的強度が脆弱になる恐れがある。従って、本発明において０≦ｂ≦３０であり、０≦ｂ≦２０であることがより好ましい。非晶質金属薄帯において、ＣｏのＦｅ置換は飽和磁化の増加に寄与する傾向にある。従って、本発明において０≦ｃ≦０．３であり、０≦ｃ≦０．２５であることがより好ましい。
【００１８】
本発明において用いる非晶質合金薄帯の厚さは、特に限定されるものではないが、５〜５０ミクロンであることが好ましく、１０〜３０ミクロンであることがより好ましい。この範囲を外れると、本発明の効果が十分に得られなくなる恐れがある。
【００１９】
本発明の非晶質合金薄帯積層体は、閉磁路系で測定される周波数１００ｋＨｚにおける該非晶質合金薄帯積層体の比透磁率μが１２，０００以上であり、かつコア損失Ｐｃが１２Ｗ／ｋｇ以下である。より好ましくは、本発明の非晶質合金薄帯積層体は、閉磁路系で測定される周波数１００ｋＨｚにおける該非晶質合金薄帯積層体の比透磁率μが１４，０００以上であり、かつコア損失Ｐｃが１１Ｗ／ｋｇ以下であり、さらに好ましくは比透磁率μが１６，０００以上であり、かつコア損失Ｐｃが１０Ｗ／ｋｇ以下である。閉磁路系での比透磁率μおよびコア損失Ｐｃの測定方法としては、一般的な手法を用いることができるが、本発明においては、リング形状を好適に用いられる。具体的には、リングの厚さ方向が積層体の積層端面となる様にし、リングの寸法は、内径５〜１００ミリメートル、外径１０〜３００ミリメートル、厚さ１０〜１０００ミクロンの範囲が好適に用いられる。本発明における比透磁率μの測定条件は、ｓｉｎ波形で印加磁界５ミリエルステッドであり、本発明におけるコア損失Ｐｃの測定条件は、ｓｉｎ波形で最大磁束密度０．１テスラである。
【００２０】
本発明の非晶質合金薄帯積層体は、引っ張り強度が３０ＭＰａ以上である。より好ましくは、本発明の非晶質合金薄帯積層体は、引っ張り強度が５０ＭＰａ以上である。引っ張り強度の測定は、日本工業規格ＪＩＳ−Ｋ７１２７に準ずる。この規格においてはサンプルの厚さに規定はなく、１ミリメートル以下が対象となっているが、本発明においては積層体の厚さを１０〜５００ミクロンの範囲とすることが好ましい。ただし、この範囲に限定されるものではない。試験片としては、３号形試験片を採用する。予め打ち抜き等で規格に適合した試験片形状に加工して積層したサンプルでもよく、また積層体を打ち抜いたものでも良い。
【００２１】
本発明の非晶質合金薄帯積層体の製造方法として、元素組成が［Ｃｏ１−ｃ・Ｆｅｃ］１００−ａ−ｂ・Ｘａ・Ｙｂ（但し、ＸはＳｉ、Ｂ、Ｃ、Ｇｅから選ばれる少なくとも一種類以上の元素を表し、ＹはＺｒ、Ｎｂ、Ｔｉ、Ｈｆ、Ｔａ、Ｗ、Ｃｒ、Ｍｏ、Ｖ、Ｎｉ、Ｐ、Ａｌ、Ｐｔ、Ｒｈ、Ｒｕ、Ｓｎ、Ｓｂ、Ｃｕ、Ｍｎまたは希土類元素から選ばれる少なくとも一種類以上の元素を表す。またａ、ｂ、ｃはそれぞれ、１０＜ａ≦３５、０≦ｂ≦３０、０≦ｃ≦０．３で表される数である。）で表される非晶質合金薄帯の片面または両面に樹脂層を形成させた複合薄帯を重ね合わせ、圧力０．０１〜１００ＭＰａ、温度３５０〜４８０℃、時間１〜３００分の条件で積層接着および焼鈍を同時に行う方法を好適に用いることができる。
【００２２】
複合薄帯を積層接着および焼鈍を同時に行う際の圧力条件は、０．０１〜１００ＭＰａが好ましく、０．０３〜２０ＭＰａがより好ましく、０．１〜３ＭＰａがさらに好ましい。０．０１ＭＰａ未満であると、十分接着が行われず積層体の引っ張り強度が低減するなどの問題が生じる恐れがあり、１００ＭＰａを超えると、比透磁率が低減したりコア損失が増大するなど、優れた磁気特性が得られないなどの問題が生じる恐れがある。また複合薄帯を積層接着および焼鈍を同時に行う際の温度条件は、３５０〜４８０℃が好ましく、３８０〜４５０℃がより好ましく、４００〜４４０℃がさらに好ましい。３５０℃未満あるいは４８０℃を超えると、適切な焼鈍が行われないなどの原因により、優れた磁気特性が得られないなどの問題が生じる恐れがある。また複合薄帯を積層接着および焼鈍を同時に行う際の時間条件は、１〜３００分が好ましく、５〜２００分がより好ましく、１０〜１２０分がさらに好ましい。１分未満あるいは３００分を超えると、適切な焼鈍が行われないなどの原因により、優れた磁気特性が得られないなどの問題が生じたり、十分接着が行われず積層体の引っ張り強度が低減するなどの問題が生じる恐れがある。
【００２３】
複合薄帯を積層接着および焼鈍を同時に行う方法は特に限定されるものではなく、例えば熱プレス法、器具などを用いて積層固定して加熱する方法などを好適に挙げることができる。また、積層接着および焼鈍を同時に行う際には、窒素などの不活性ガス雰囲気で行うことが好ましい。
【００２４】
本発明の非晶質合金薄帯積層体の製造方法として、［Ｃｏ１−ｃ・Ｆｅｃ］１００−ａ−ｂ・Ｘａ・Ｙｂ（但し、ＸはＳｉ、Ｂ、Ｃ、Ｇｅから選ばれる少なくとも一種類以上の元素を表し、ＹはＺｒ、Ｎｂ、Ｔｉ、Ｈｆ、Ｔａ、Ｗ、Ｃｒ、Ｍｏ、Ｖ、Ｎｉ、Ｐ、Ａｌ、Ｐｔ、Ｒｈ、Ｒｕ、Ｓｎ、Ｓｂ、Ｃｕ、Ｍｎまたは希土類元素から選ばれる少なくとも一種類以上の元素を表す。またａ、ｂ、ｃはそれぞれ、１０＜ａ≦３５、０≦ｂ≦３０、０≦ｃ≦０．３で表される数である。）で表される非晶質合金薄帯の片面または両面に樹脂層を形成させた複合薄帯を重ね合わせ、圧力０．０１〜５００ＭＰａ、温度２００〜３５０℃、時間１〜３００分の条件で積層接着を行い、次いで圧力０〜１００ＭＰａ、温度３５０〜４８０℃、時間１〜３００分の条件で焼鈍を行う方法を好適に用いることができる。
【００２５】
複合薄帯を積層接着する際の圧力条件は、０．０１〜５００ＭＰａが好ましく、０．０３〜２００ＭＰａがより好ましく、０．１〜１００ＭＰａがさらに好ましい。０．０１ＭＰａ未満であると、十分接着が行われず積層体の引っ張り強度が低減するなどの問題が生じる恐れがあり、５００ＭＰａを超えると、比透磁率が低減したりコア損失が増大するなど、優れた磁気特性が得られないなどの問題が生じる恐れがある。また複合薄帯を積層接着する際の温度条件は、２００〜３５０℃が好ましく、２５０〜３００℃がより好ましい。２００℃未満であると、十分接着が行われず積層体の引っ張り強度が低減するなどの問題が生じる恐れがあり、３５０℃を超えると、比透磁率が低減したりコア損失が増大するなど、優れた磁気特性が得られないなどの問題が生じる恐れがある。また複合薄帯を積層接着する際の時間条件は、１〜３００分が好ましく、５〜２００分がより好ましく、１０〜１２０分がさらに好ましい。１分未満あるいは３００分を超えると、適切な積層接着が行われないなどの原因により、積層体の引っ張り強度が低減するなどの問題が生じる恐れがある。
【００２６】
積層接着した積層体を焼鈍する際の圧力条件は、０〜１００ＭＰａが好ましく、０〜２０ＭＰａがより好ましく、０〜１０ＭＰａがさらに好ましい。１００ＭＰａを超えると、比透磁率が低減したりコア損失が増大するなど、優れた磁気特性が得られないなどの問題が生じる恐れがある。また積層接着した積層体を焼鈍する際の温度条件は、３５０〜４８０℃が好ましく、３８０〜４５０℃がより好ましく、４００〜４４０℃がさらに好ましい。３５０℃未満あるいは４８０℃を超えると、適切な焼鈍が行われないなどの原因により、優れた磁気特性が得られないなどの問題が生じる恐れがある。また積層接着した積層体を焼鈍する際の時間条件は、１〜３００分が好ましく、５〜２００分がより好ましく、１０〜１２０分がさらに好ましい。１分未満あるいは３００分を超えると、適切な焼鈍が行われないなどの原因により、優れた磁気特性が得られないなどの問題が生じる恐れがある。
【００２７】
複合薄帯を積層接着または焼鈍を行う方法は特に限定されるものではなく、例えば熱プレス法、器具などを用いて積層固定して加熱する方法などを好適に挙げることができる。また、積層接着および焼鈍を行う際には、窒素などの不活性ガス雰囲気で行うことが好ましい。
【００２８】
非晶質合金薄帯の片面または両面に樹脂層を形成させた複合薄帯の製造方法は、特に限定されるものではなく、例えば非晶質合金薄帯に樹脂または樹脂の前駆体が溶解した溶液を薄く塗布し、溶剤を乾燥させる方法などを好適に用いることができる。
【００２９】
本発明の非晶質合金薄帯積層体において、積層接着の媒体として用いる樹脂としては、熱可塑性の耐熱樹脂が好適に用いられる。その特性は、本発明の効果が得られる範囲であれば特に限定されるものではないが、窒素雰囲気下３６５℃、２時間の熱履歴を経た後の３０℃における引っ張り強度が３０ＭＰａ以上であり、かつ窒素雰囲気下３６５℃、２時間の熱履歴を経た際の熱分解による重量減少率が２重量％以下である特性を有する熱可塑性樹脂を好適に用いることができる。具体的には、ポリイミド系樹脂、ポリエーテルイミド系樹脂、ポリアミドイミド系樹脂、ポリアミド系樹脂、ポリスルホン系樹脂、ポリエーテルケトン系樹脂を好適に用いることができ、より具体的には化学式（１）〜（１０）で表される繰り返し単位を主鎖骨格に有する樹脂を好適に用いることができる。但し、化学式（１）においてｄおよびｅは、ｄ＋ｅ＝１、０≦ｄ≦１、０≦ｅ≦１を満たす数であり、ＱおよびＲは、直接結合、エーテル結合、イソプロピリデン結合、スルフィド結合、スルホン結合、並びにカルボニル結合から選ばれる結合基で、同一でも異なっていても良い。また化学式（２）においてＴは、直接結合、エーテル結合、イソプロピリデン結合、スルフィド結合、スルホン結合、並びにカルボニル結合から選ばれる結合基である。また化学式（６）においてｆおよびｇは、ｆ＋ｇ＝１、０≦ｆ≦１、０≦ｇ≦１を満たす数である。）。
【００３０】
【化１】
本発明の非晶質合金薄帯積層体は、Ｃｏ系非晶質合金薄帯が本来有する優れた磁気性能に機械強度を加味した優れた磁性材料であり、従来技術では得ることができないものである。
【００３２】
本発明の非晶質合金薄帯積層体は、それを含んで構成される磁気応用部品として好適に用いることができる。より具体的には、例えばインダクタンス、各種コイル、各種トランス、ノイズフィルター、磁気センサー、磁気ヘッド、アンテナ、電波吸収体、モーター、各種コア、配線基板に好適に用いることができる。
【００３３】
【実施例】
以下、本発明を実施例により詳細に説明する。なお、実施例等における諸物性等の測定は、以下の方法により行った。
・磁気特性評価用のリング：非晶質合金薄帯の片面に樹脂層を形成した複合薄帯を、内径２５ミリメートル、外径４０ミリメートルに打ち抜き、５枚を重ねて所定の条件で加熱積層して得た。
・比透磁率μ：周波数１００ｋＨｚ、ｓｉｎ波形で印加電界５ミリエルステッドの条件で、インピー ダンスアナライザー（ＹＨＰ ４１９２Ａ ＬＦ）により測定した。
・コア損失Ｐｃ：周波数１００ｋＨｚ、ｓｉｎ波形で最大磁束密度０．１テスラの条件で、Ｂ−Ｈアナライザー（ＩＷＡＴＳＵ ＳＹ−８２１６）により測定した。
・引っ張り強度：日本工業規格ＪＩＳ−Ｋ７１２７に準じて測定した。非晶質合金薄帯の片面に樹脂層を形成した複合薄帯を、打ち抜きにより３号形試験片状に加工し、２０枚を重ねて所定の条件で加熱積層して試験片を作製し、測定に供した。
【００３４】
【合成例】
米国ハネウェル社製の非晶質合金薄帯Ｍｅｔｇｌａｓ２７１４Ａ（元素比Ｃｏ：Ｆｅ：Ｎｉ：Ｓｉ：Ｂ＝６６：４：１：１５：１４）の片面に、化学式（１１）で表される繰り返し単位を主鎖骨格に有するポリアミド酸が２０重量％溶解した溶液（溶媒：Ｎ，Ｎ―ジメチルアセトアミド）を薄く塗布し、加熱によって溶媒の除去と熱イミド化を行った。得られた複合薄帯は、幅５０ミリメートル、合金層が平均１６．５ミクロン、イミド樹脂層が平均４ミクロンであった。
【００３５】
【化２】
【参考例１】
米国ハネウェル社製の非晶質合金薄帯Ｍｅｔｇｌａｓ２７１４Ａ（元素比Ｃｏ：Ｆｅ：Ｎｉ：Ｓｉ：Ｂ＝６６：４：１：１５：１４）を、比透磁率ならびにコア損失測定用にリング状に打ち抜き、何も処理することなく比透磁率ならびにコア損失を測定した。その結果、比透磁率は７，２８０、コア損失２１．１Ｗ／ｋｇであった。また引っ張り強度は１０２０ＭＰａであった。結果を表１および表２に示す。
【００３７】
【参考例２】
米国ハネウェル社製の非晶質合金薄帯Ｍｅｔｇｌａｓ２７１４Ａ（元素比Ｃｏ：Ｆｅ：Ｎｉ：Ｓｉ：Ｂ＝６６：４：１：１５：１４）を、比透磁率ならびにコア損失測定用にリング状に打ち抜き、無加圧、温度４００℃、時間６０分の条件で焼鈍処理した。熱処理は一般的なチューブ型の加熱炉を用い、窒素雰囲気で行うために窒素を毎分０．５リットル通流しながら実施した。なお、樹脂層を形成した複合薄帯ではないため、実際には接着せず積層体とはなっていない。薄帯を５枚重ねて測定した。結果を表１に示す。比透磁率は１２，１３０と高く、またコア損失は１０．８Ｗ／ｋｇと低く、Ｃｏ系非晶質合金薄帯が優れた磁気特性を有していることを確認した。しかしながら得られた薄帯は非常に脆く、慎重に取り扱わなければ破損する程度であり、引っ張り強度は測定することができなかった。
【００３８】
【参考例３〜４】
参考例２と同様にして、表１に示した条件で熱処理を行い、磁気特性等を評価した。結果を表１に示す。
【００３９】
【実施例１】
合成例で示した複合薄帯を、比透磁率ならびにコア損失測定用にリング状、引っ張り強度測定用にＪＩＳ規格の試験片状に打ち抜いた。リング状のものは５枚、試験片状のものは２０枚を同じ向きで重ね、熱プレス機（ＴＯＹＯＳＥＩＫＩミニテストプレス タイプＷＣＨ）を用いて、圧力１ＭＰａ、温度４００℃、時間６０分の条件で積層接着および焼鈍を同時に行った。なお窒素雰囲気で行うために、タンケンシールセーコウ社製のボディーフレームを用いて、窒素を毎分０．５リットル通流しながら実施した。磁気特性を測定したところ、比透磁率は２１，６８０、コア損失７．３Ｗ／ｋｇであり、同条件で処理した非晶質合金薄帯のみの磁気特性よりも優れた性能を有していた。また、引っ張り強度は１１０ＭＰａであり、機械的強度も優れるものであった。結果を表１に示す。
【００４０】
【実施例２〜７】
実施例１と同様にして、表１に示した条件で積層接着および焼鈍を同時に行い、評価した。結果を表１に示す。
【００４１】
【比較例１〜６】
実施例１と同様にして、表１に示した条件で積層接着および焼鈍を同時に行い、評価した。結果を表１に示す。
【００４２】
【参考例５】
米国ハネウェル社製の非晶質合金薄帯Ｍｅｔｇｌａｓ２７１４Ａ（元素比Ｃｏ：Ｆｅ：Ｎｉ：Ｓｉ：Ｂ＝６６：４：１：１５：１４）を、比透磁率ならびにコア損失測定用にリング状に打ち抜き、圧力１０ＭＰａ、温度２５０℃、時間３０分の条件で、熱プレス機（ＴＯＹＯＳＥＩＫＩ ミニテストプレス タイプＷＣＨ）を用いて加圧熱処理した。なお窒素雰囲気で行うために、タンケンシールセーコウ社製のボディーフレームを用いて、窒素を毎分０．５リットル通流しながら実施した。一度冷却した後、次いで無加圧、温度４２０℃、時間６０分の条件で熱処理を行った。この熱処理は一般的なチューブ型の加熱炉を用い、窒素雰囲気で行うために窒素を毎分０．５リットル通流しながら実施した。なお、樹脂層を形成した複合薄帯ではないため、実際には接着せず積層体とはなっていない。薄帯を５枚重ねて測定した。結果を表２に示す。比透磁率は１５，１２０と高く、またコア損失は９．８Ｗ／ｋｇと低く、Ｃｏ系非晶質合金薄帯が優れた磁気特性を有していることを確認した。しかしながら得られた薄帯は非常に脆く、慎重に取り扱わなければ破損する程度であり、引っ張り強度は測定することができなかった。
【００４３】
【実施例８】
合成例で示した複合薄帯を、比透磁率ならびにコア損失測定用にリング状、引っ張り強度測定用にＪＩＳ規格の試験片状に打ち抜いた。リング状のものは５枚、試験片状のものは２０枚を同じ向きで重ね、熱プレス機（ＴＯＹＯＳＥＩＫＩミニテストプレス タイプＷＣＨ）を用いて、圧力１０ＭＰａ、温度２５０℃、時間３０分の条件で積層接着して積層体を得た。なお窒素雰囲気で行うために、タンケンシールセーコウ社製のボディーフレームを用いて、窒素を毎分０．５リットル通流しながら実施した。一度冷却した後、次いで無加圧、温度４２０℃、時間６０分の条件で熱処理を行った。この熱処理は一般的なチューブ型の加熱炉を用い、窒素雰囲気で行うために窒素を毎分０．５リットル通流しながら実施した。磁気特性を測定したところ、比透磁率は１４，７８０、コア損失９．９Ｗ／ｋｇであり、同条件で処理した非晶質合金薄帯のみの磁気特性と同レベルの優れた性能を有していた。また、引っ張り強度は１０２ＭＰａであり、機械的強度も優れるものであった。結果を表２に示す。
【００４４】
【実施例９〜１３】
実施例８と同様にして、表２に示した条件で積層接着、次いで焼鈍を行い、評価した。結果を表２に示す。
【００４５】
【比較例７〜１１】
実施例８と同様にして、表２に示した条件で積層接着、次いで焼鈍を行い、評価した。結果を表２に示す。
【００４６】
【表１】
【表２】
【発明の効果】
本発明の非晶質合金薄帯積層体は、Ｃｏ系非晶質合金薄帯が本来有する優れた磁気特性と機械的強度を併せ持つ材料であり、従来技術では達成することができなかった性能を有する材料である。本発明の非晶質合金薄帯積層体は、非晶質合金薄帯としてＣｏ系非晶質合金薄帯を用い、特定の圧力、温度、時間の条件において積層接着させることにより、また特定の圧力、温度、時間の条件において積層接着させ、次いで特定の圧力、温度、時間の条件において焼鈍させることにより、製造することができる。本発明の非晶質合金薄帯積層体は、それを含んで構成される磁気応用部品として好適に用いることができ、具体的には、例えばインダクタンス、各種コイル、各種トランス、ノイズフィルター、磁気センサー、磁気ヘッド、アンテナ、電波吸収体、モーター、各種コア、配線基板に好適に用いることができる。[0001]
[Industrial application fields]
The present invention relates to an amorphous alloy ribbon laminated body in which amorphous alloy ribbons are laminated and bonded using a resin as a medium, and more specifically, an amorphous alloy having both excellent magnetic performance and strength as a magnetic application part. The present invention relates to a ribbon laminate.
[0002]
[Prior art]
An amorphous alloy ribbon is an amorphous solid produced by rapidly cooling various metals into raw materials from a molten state, and is usually a ribbon having a thickness of about 0.01 to 0.1 mm. is there. In these amorphous alloy ribbons, atoms have a random structure with no regular arrangement, and have excellent characteristics as a soft magnetic material. In particular, a Co-based amorphous alloy ribbon containing Co element is a material having both high relative permeability and low core loss, and various magnetic application parts such as inductance, various coils, various transformers, noise filters, magnetic sensors. It is expected to be used in a wide range of fields such as magnetic heads, antennas, radio wave absorbers, motors, various cores, and wiring boards.
[0003]
The amorphous alloy ribbon is generally subjected to a predetermined annealing heat treatment in order to develop its excellent magnetic properties. The annealing heat treatment conditions vary depending on the magnetic properties to be expressed and the type of amorphous alloy, but are generally performed at a high temperature and a long time of about 300 to 500 ° C. for about 0.1 to 100 hours in an inert atmosphere. Is common. However, although it exhibits excellent magnetic properties by annealing heat treatment, it has a problem that it becomes an extremely fragile ribbon and becomes physically difficult to handle.
[0004]
As a method for dealing with this problem, a method of laminating and bonding amorphous alloy ribbons using a heat-resistant polymer compound that can withstand annealing temperatures such as polyimide resin as an adhesive is disclosed (Patent Document 1). According to this method, since adhesion lamination with a heat-resistant resin can be performed simultaneously with annealing, the problem of handling a fragile ribbon can be solved. However, use of a heat resistant resin causes unnecessary stress in the amorphous alloy ribbon, and a new problem arises in that the magnetic properties are reduced as compared with the case where no resin is used. That is, the excellent magnetic properties inherent to the amorphous alloy ribbon cannot be sufficiently exhibited. In addition, only a core in which an Fe-based amorphous alloy ribbon is laminated by winding is being studied, and in order to fully develop the magnetic characteristics of the Co-based amorphous alloy ribbon. This technique is not disclosed at all.
[0005]
As described above, it is the actual situation that a material having mechanical strength while having the excellent magnetic properties inherent in the amorphous alloy ribbon has not yet been found, and its development is desired.
[0006]
[Patent Document 1]
JP 58-175654 A
[0007]
[Problems to be solved by the present invention]
In view of the above-mentioned problems of the prior art, an object of the present invention is to provide an amorphous alloy ribbon laminate having excellent magnetic properties and mechanical strength inherent in a Co-based amorphous alloy ribbon, and a method for producing the same. It is to provide.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an amorphous alloy thin ribbon in which an amorphous alloy ribbon is laminated and bonded using a resin as a medium. By using a Co-based amorphous alloy ribbon as a band, by simultaneously performing lamination adhesion and annealing under specific conditions, or by performing lamination adhesion under specific conditions, and then annealing under specific conditions, The present inventors have found that an amorphous alloy ribbon laminated body having both the excellent magnetic properties inherent in the amorphous alloy ribbon and mechanical strength has been completed.
[0009]
That is, this invention is specified by the matter described in the following [1]-[6].
[0010]
[1] In an amorphous alloy ribbon laminate in which amorphous alloy ribbons are laminated and bonded using a resin as a medium, the elemental composition of the amorphous alloy is [Co 1-c ・ Fe c ] 100-ab ・ X a ・ Y b (However, X represents at least one element selected from Si, B, C, and Ge, and Y represents Zr, Nb, Ti, Hf, Ta, W, Cr, Mo, V, Ni, P, Al, Pt, R It represents at least one element selected from h, Ru, Sn, Sb, Cu, Mn or rare earth elements. A, b, and c are numbers represented by 10 <a ≦ 35, 0 ≦ b ≦ 30, and 0 ≦ c ≦ 0.3, respectively. The relative permeability μ of the amorphous alloy ribbon laminated body at a frequency of 100 kHz measured in a closed magnetic circuit system is 12,000 or more and the core loss Pc is 12 W / kg or less. An amorphous alloy ribbon laminate, wherein the ribbon laminate has a tensile strength of 30 MPa or more.
[0011]
[2] Elemental composition is [Co 1-c ・ Fe c ] 100-ab ・ X a ・ Y b (However, X represents at least one element selected from Si, B, C, and Ge, and Y represents Zr, Nb, Ti, Hf, Ta, W, Cr, Mo, V, Ni, P, Al, Pt, R It represents at least one element selected from h, Ru, Sn, Sb, Cu, Mn or rare earth elements. A, b, and c are numbers represented by 10 <a ≦ 35, 0 ≦ b ≦ 30, and 0 ≦ c ≦ 0.3, respectively. The composite ribbon in which a resin layer is formed on one side or both sides of the amorphous alloy ribbon represented by the above is superposed, and the pressure is 0.01 to 100 MPa, the temperature is 350 to 480 ° C., and the time is 1 to 300 minutes. A method for producing an amorphous alloy ribbon laminate in which an amorphous alloy ribbon is laminated and bonded using a resin as a medium, wherein the lamination adhesion and annealing are performed simultaneously.
[0012]
[3] Elemental composition is [Co 1-c ・ Fe c ] 100-ab ・ X a ・ Y b (However, X represents at least one element selected from Si, B, C, and Ge, and Y represents Zr, Nb, Ti, Hf, Ta, W, Cr, Mo, V, Ni, P, Al, Pt, R It represents at least one element selected from h, Ru, Sn, Sb, Cu, Mn or rare earth elements. A, b, and c are numbers represented by 10 <a ≦ 35, 0 ≦ b ≦ 30, and 0 ≦ c ≦ 0.3, respectively. The composite ribbon in which a resin layer is formed on one side or both sides of the amorphous alloy ribbon represented by) is superposed, and the pressure is 0.01 to 500 MPa, the temperature is 200 to 350 ° C., and the time is 1 to 300 minutes. Laminate bonding is performed, and then annealing is performed under conditions of a pressure of 0 to 100 MPa, a temperature of 350 to 480 ° C., and a time of 1 to 300 minutes. A method for producing a crystalline alloy ribbon laminate.
[0013]
[4] An amorphous alloy ribbon laminated body in which amorphous alloy ribbons are laminated and bonded using the resin produced by the method of [2] or [3] as a medium.
[0014]
[5] The amorphous alloy ribbon laminate according to claim 1, which is produced by the method according to [2] or [3].
[0015]
[6] A magnetic application part comprising the amorphous alloy ribbon laminated body according to [1], [4] or [5].
[0016]
DETAILED DESCRIPTION OF THE INVENTION
The amorphous alloy ribbon laminate of the present invention is an amorphous alloy ribbon laminate in which amorphous alloy ribbons are laminated and bonded using a resin as a medium.
[0017]
The amorphous alloy ribbon used in the present invention has an elemental composition of [Co 1-c ・ Fe c ] 100-ab ・ X a ・ Y b It is represented by X represents at least one element selected from Si, B, C, and Ge, and Y represents Zr, Nb, Ti, Hf, Ta, W, Cr, Mo, V, Ni, P, Al, and Pt. , R It represents at least one element selected from h, Ru, Sn, Sb, Cu, Mn or rare earth elements. A, b, and c are numbers represented by 10 <a ≦ 35, 0 ≦ b ≦ 30, and 0 ≦ c ≦ 0.3, respectively. Element X is an effective element for reducing the crystallization speed for making amorphous when producing an amorphous alloy ribbon. If a is less than 10, amorphization may be reduced and some crystalline may be mixed. If a exceeds 35, an amorphous structure is obtained, but the mechanical strength of the alloy ribbon is obtained. May decrease, and a continuous ribbon may not be obtained. Therefore, in the present invention, 10 <a ≦ 35 and 12 ≦ a ≦ 30 are more preferable. Element Y is effective in the corrosion resistance of the amorphous alloy ribbon. Among these, particularly effective elements are Zr, Nb, Mn, W, Mo, Cr, V, Ni, P, Al, Pt, Ru , Rh. If b exceeds 30, the mechanical strength of the amorphous alloy ribbon may be fragile. Therefore, in the present invention, 0 ≦ b ≦ 30 and more preferably 0 ≦ b ≦ 20. In an amorphous metal ribbon, Co substitution of Fe tends to contribute to an increase in saturation magnetization. Therefore, in the present invention, 0 ≦ c ≦ 0.3 and more preferably 0 ≦ c ≦ 0.25.
[0018]
The thickness of the amorphous alloy ribbon used in the present invention is not particularly limited, but is preferably 5 to 50 microns, and more preferably 10 to 30 microns. Outside this range, the effects of the present invention may not be sufficiently obtained.
[0019]
The amorphous alloy ribbon laminate of the present invention has a relative magnetic permeability μ of 12,000 or more and a core loss Pc of 12 W at a frequency of 100 kHz measured in a closed magnetic circuit system. / Kg or less. More preferably, in the amorphous alloy ribbon laminate of the present invention, the relative permeability μ of the amorphous alloy ribbon laminate at a frequency of 100 kHz measured by a closed magnetic path system is 14,000 or more, and the core The loss Pc is 11 W / kg or less, more preferably the relative permeability μ is 16,000 or more, and the core loss Pc is 10 W / kg or less. As a method of measuring the relative magnetic permeability μ and the core loss Pc in the closed magnetic circuit system, a general method can be used, but in the present invention, a ring shape is preferably used. Specifically, the ring thickness direction is the end face of the laminate, and the ring dimensions are preferably in the range of 5-100 mm inner diameter, 10-300 mm outer diameter, and 10-1000 microns in thickness. Used. The measurement condition of the relative permeability μ in the present invention is an applied magnetic field of 5 millielsted in a sin waveform, and the measurement condition of the core loss Pc in the present invention is a maximum magnetic flux density of 0.1 Tesla in a sin waveform.
[0020]
The amorphous alloy ribbon laminate of the present invention has a tensile strength of 30 MPa or more. More preferably, the amorphous alloy ribbon laminated body of the present invention has a tensile strength of 50 MPa or more. The measurement of tensile strength is based on Japanese Industrial Standard JIS-K7127. In this standard, the thickness of the sample is not specified, and is 1 mm or less, but in the present invention, the thickness of the laminate is preferably in the range of 10 to 500 microns. However, it is not limited to this range. A No. 3 type test piece is employed as the test piece. It may be a sample that has been processed into a test piece shape that conforms to the standard by punching or the like and laminated, or a laminate that has been punched out.
[0021]
As a method for producing the amorphous alloy ribbon laminate of the present invention, the elemental composition is [Co 1-c ・ Fe c ] 100-ab ・ X a ・ Y b (However, X represents at least one element selected from Si, B, C, and Ge, and Y represents Zr, Nb, Ti, Hf, Ta, W, Cr, Mo, V, Ni, P, Al, Pt, R It represents at least one element selected from h, Ru, Sn, Sb, Cu, Mn or rare earth elements. A, b, and c are numbers represented by 10 <a ≦ 35, 0 ≦ b ≦ 30, and 0 ≦ c ≦ 0.3, respectively. The composite ribbon in which a resin layer is formed on one side or both sides of the amorphous alloy ribbon represented by the above is superposed, and the pressure is 0.01 to 100 MPa, the temperature is 350 to 480 ° C., and the time is 1 to 300 minutes. A method of simultaneously performing lamination adhesion and annealing can be preferably used.
[0022]
The pressure condition for simultaneously laminating and annealing the composite ribbon is preferably 0.01 to 100 MPa, more preferably 0.03 to 20 MPa, and still more preferably 0.1 to 3 MPa. If it is less than 0.01 MPa, sufficient adhesion may not be performed and problems such as reduction in the tensile strength of the laminate may occur, and if it exceeds 100 MPa, the relative permeability is reduced or the core loss is increased. There is a risk that problems such as inability to obtain magnetic characteristics may occur. Moreover, 350-480 degreeC is preferable, as for the temperature conditions at the time of carrying out lamination | stacking adhesion | attachment and annealing of a composite ribbon simultaneously, 380-450 degreeC is more preferable, 400-440 degreeC is further more preferable. If it is less than 350 ° C. or exceeds 480 ° C., there is a possibility that problems such as inability to obtain excellent magnetic properties due to a cause such as failure of proper annealing. Moreover, 1 to 300 minutes are preferable, as for the time conditions at the time of performing lamination | stacking adhesion | attachment and annealing simultaneously with a composite ribbon, 5 to 200 minutes are more preferable, and 10 to 120 minutes are more preferable. If less than 1 minute or more than 300 minutes, problems such as inability to obtain excellent magnetic properties due to failure to perform appropriate annealing, or insufficient adhesion is not achieved, and the tensile strength of the laminate is reduced. May cause problems.
[0023]
A method of simultaneously laminating and annealing the composite ribbon is not particularly limited, and examples thereof include a method of laminating and fixing using a hot press method, an instrument, and the like. Moreover, when performing lamination | stacking adhesion | attachment and annealing simultaneously, it is preferable to carry out in inert gas atmosphere, such as nitrogen.
[0024]
As a method for producing an amorphous alloy ribbon laminate of the present invention, [Co 1-c ・ Fe c ] 100-ab ・ X a ・ Y b (However, X represents at least one element selected from Si, B, C, and Ge, and Y represents Zr, Nb, Ti, Hf, Ta, W, Cr, Mo, V, Ni, P, Al, Pt, R It represents at least one element selected from h, Ru, Sn, Sb, Cu, Mn or rare earth elements. A, b, and c are numbers represented by 10 <a ≦ 35, 0 ≦ b ≦ 30, and 0 ≦ c ≦ 0.3, respectively. The composite ribbon in which a resin layer is formed on one side or both sides of the amorphous alloy ribbon represented by the above is superposed, and the pressure is 0.01 to 500 MPa, the temperature is 200 to 350 ° C., and the time is 1 to 300 minutes. A method of performing lamination bonding and then annealing under conditions of a pressure of 0 to 100 MPa, a temperature of 350 to 480 ° C., and a time of 1 to 300 minutes can be suitably used.
[0025]
The pressure condition for laminating and bonding the composite ribbon is preferably 0.01 to 500 MPa, more preferably 0.03 to 200 MPa, and further preferably 0.1 to 100 MPa. If it is less than 0.01 MPa, adhesion may not be performed sufficiently and problems such as reduction in the tensile strength of the laminate may occur, and if it exceeds 500 MPa, the relative permeability is reduced or the core loss is increased. There is a risk that problems such as inability to obtain magnetic characteristics may occur. The temperature condition for laminating and bonding the composite ribbon is preferably 200 to 350 ° C, more preferably 250 to 300 ° C. If the temperature is less than 200 ° C, sufficient adhesion may not be performed and problems such as a decrease in the tensile strength of the laminate may occur. If the temperature exceeds 350 ° C, the relative permeability may decrease or the core loss may increase. There is a risk that problems such as inability to obtain magnetic characteristics may occur. The time condition for laminating and bonding the composite ribbon is preferably 1 to 300 minutes, more preferably 5 to 200 minutes, and still more preferably 10 to 120 minutes. If it is less than 1 minute or more than 300 minutes, there is a possibility that problems such as reduction in the tensile strength of the laminate may occur due to the failure to perform proper lamination adhesion.
[0026]
0-100 MPa is preferable, as for the pressure conditions at the time of annealing the laminated body which carried out lamination | stacking adhesion, 0-20 MPa is more preferable, and 0-10 MPa is more preferable. When it exceeds 100 MPa, there is a possibility that problems such as inability to obtain excellent magnetic properties such as reduction in relative permeability and increase in core loss may occur. Moreover, 350-480 degreeC is preferable, as for the temperature conditions at the time of annealing the laminated body which carried out lamination | stacking adhesion, 380-450 degreeC is more preferable, and 400-440 degreeC is further more preferable. If it is less than 350 ° C. or exceeds 480 ° C., there is a possibility that problems such as inability to obtain excellent magnetic properties may occur due to the reason that appropriate annealing is not performed. Moreover, 1 to 300 minutes are preferable, as for the time conditions at the time of annealing the laminated body which carried out lamination | stacking adhesion, 5 to 200 minutes are more preferable, and 10 to 120 minutes are more preferable. If it is less than 1 minute or more than 300 minutes, there is a possibility that problems such as inability to obtain excellent magnetic properties due to causes such as failure of proper annealing.
[0027]
A method for laminating or annealing the composite ribbon is not particularly limited, and examples thereof include a method of laminating and fixing using a hot press method, an instrument, and the like. Moreover, when performing lamination | stacking adhesion | attachment and annealing, it is preferable to carry out in inert gas atmosphere, such as nitrogen.
[0028]
The method for producing a composite ribbon in which a resin layer is formed on one or both sides of an amorphous alloy ribbon is not particularly limited. For example, a resin or a resin precursor is dissolved in an amorphous alloy ribbon. A method of applying the solution thinly and drying the solvent can be suitably used.
[0029]
In the amorphous alloy ribbon laminated body of the present invention, a thermoplastic heat-resistant resin is suitably used as the resin used as a medium for lamination adhesion. The characteristics are not particularly limited as long as the effect of the present invention is obtained, but the tensile strength at 30 ° C. after passing through a heat history of 365 ° C. and 2 hours in a nitrogen atmosphere is 30 MPa or more, In addition, a thermoplastic resin having a characteristic that the weight reduction rate due to thermal decomposition at 365 ° C. for 2 hours in a nitrogen atmosphere is 2% by weight or less can be suitably used. Specifically, a polyimide resin, a polyetherimide resin, a polyamideimide resin, a polyamide resin, a polysulfone resin, or a polyetherketone resin can be suitably used. More specifically, the chemical formula (1) Resins having a repeating unit represented by (10) in the main chain skeleton can be preferably used. However, in chemical formula (1), d and e are numbers satisfying d + e = 1, 0 ≦ d ≦ 1, 0 ≦ e ≦ 1, and Q and R are direct bond, ether bond, isopropylidene bond, sulfide bond , A sulfone bond, and a carbonyl bond, which may be the same or different. In chemical formula (2), T is a linking group selected from a direct bond, an ether bond, an isopropylidene bond, a sulfide bond, a sulfone bond, and a carbonyl bond. In chemical formula (6), f and g are numbers satisfying f + g = 1, 0 ≦ f ≦ 1, and 0 ≦ g ≦ 1. ).
[0030]
[Chemical 1]
The amorphous alloy ribbon laminated body of the present invention is an excellent magnetic material in which mechanical strength is added to the excellent magnetic performance inherent in the Co-based amorphous alloy ribbon, and cannot be obtained by the prior art. is there.
[0032]
The amorphous alloy ribbon laminated body of the present invention can be suitably used as a magnetic application part including the laminated body. More specifically, for example, it can be suitably used for inductance, various coils, various transformers, noise filters, magnetic sensors, magnetic heads, antennas, radio wave absorbers, motors, various cores, and wiring boards.
[0033]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples. In addition, various physical properties and the like in Examples and the like were measured by the following methods.
・ Ring for magnetic property evaluation: A composite ribbon in which a resin layer is formed on one side of an amorphous alloy ribbon is punched into an inner diameter of 25 mm and an outer diameter of 40 mm, and five layers are stacked and heated under predetermined conditions. I got it.
Specific permeability μ: measured with an impedance analyzer (YHP 4192A LF) under the conditions of a frequency of 100 kHz, a sin waveform, and an applied electric field of 5 millielsted.
Core loss Pc: Measured with a BH analyzer (IWATSU SY-8216) under conditions of a frequency of 100 kHz, a sin waveform and a maximum magnetic flux density of 0.1 Tesla.
-Tensile strength: measured according to Japanese Industrial Standard JIS-K7127. A composite ribbon in which a resin layer is formed on one surface of an amorphous alloy ribbon is processed into a No. 3 test piece by punching, and 20 pieces are stacked and heated and laminated under predetermined conditions to produce a test piece. It used for the measurement.
[0034]
[Synthesis example]
On one side of an amorphous alloy ribbon Metglas 2714A (element ratio Co: Fe: Ni: Si: B = 66: 4: 1: 15: 14) manufactured by Honeywell, USA, a repeating unit represented by the chemical formula (11) is provided. A solution (solvent: N, N-dimethylacetamide) in which 20% by weight of polyamic acid having a main chain skeleton was dissolved was thinly applied, and the solvent was removed by heating and thermal imidization was performed. The obtained composite ribbon had a width of 50 millimeters, an alloy layer averaged 16.5 microns, and an imide resin layer averaged 4 microns.
[0035]
[Chemical 2]
[Reference Example 1]
Amorphous alloy ribbon Metglas 2714A (element ratio Co: Fe: Ni: Si: B = 66: 4: 1: 15: 14) manufactured by Honeywell, USA was punched into a ring shape for measuring relative magnetic permeability and core loss. The relative permeability and core loss were measured without any treatment. As a result, the relative permeability was 7,280 and the core loss was 21.1 W / kg. The tensile strength was 1020 MPa. The results are shown in Tables 1 and 2.
[0037]
[Reference Example 2]
An amorphous alloy ribbon Metglas 2714A (element ratio Co: Fe: Ni: Si: B = 66: 4: 1: 15: 14) manufactured by Honeywell of the United States is punched into a ring shape for measuring relative permeability and core loss. Annealing was performed under the conditions of no pressure, temperature of 400 ° C. and time of 60 minutes. The heat treatment was performed using a general tube-type heating furnace with nitrogen flowing at 0.5 liters per minute in order to carry out in a nitrogen atmosphere. In addition, since it is not the composite ribbon which formed the resin layer, it does not adhere | attach but is not a laminated body. Measurement was performed with five thin ribbons stacked. The results are shown in Table 1. The relative permeability was as high as 12,130, the core loss was as low as 10.8 W / kg, and it was confirmed that the Co-based amorphous alloy ribbon has excellent magnetic properties. However, the obtained ribbon was very brittle and could be broken unless handled carefully, and the tensile strength could not be measured.
[0038]
[Reference Examples 3-4]
In the same manner as in Reference Example 2, heat treatment was performed under the conditions shown in Table 1, and magnetic characteristics and the like were evaluated. The results are shown in Table 1.
[0039]
[Example 1]
The composite ribbon shown in the synthesis example was punched into a ring shape for measuring relative permeability and core loss, and a JIS standard test piece for measuring tensile strength. 5 pieces of ring-shaped ones and 20 pieces of test piece-like ones are stacked in the same direction, and using a heat press machine (TOYOSEIKI mini test press type WCH) under the conditions of pressure 1 MPa, temperature 400 ° C., time 60 minutes. Lamination adhesion and annealing were performed simultaneously. In order to carry out in a nitrogen atmosphere, it was carried out using a body frame manufactured by Tanken Seal Seiko Co., Ltd. while passing 0.5 liters of nitrogen per minute. When the magnetic properties were measured, the relative permeability was 21,680 and the core loss was 7.3 W / kg, which was superior to the magnetic properties of only the amorphous alloy ribbon processed under the same conditions. . Moreover, the tensile strength was 110 MPa and the mechanical strength was excellent. The results are shown in Table 1.
[0040]
Examples 2-7
In the same manner as in Example 1, lamination adhesion and annealing were simultaneously performed and evaluated under the conditions shown in Table 1. The results are shown in Table 1.
[0041]
[Comparative Examples 1-6]
In the same manner as in Example 1, lamination adhesion and annealing were simultaneously performed and evaluated under the conditions shown in Table 1. The results are shown in Table 1.
[0042]
[Reference Example 5]
An amorphous alloy ribbon Metglas 2714A (element ratio Co: Fe: Ni: Si: B = 66: 4: 1: 15: 14) manufactured by Honeywell of the United States is punched into a ring shape for measuring relative permeability and core loss. Then, pressure heat treatment was performed using a hot press machine (TOYOSEIKI mini test press type WCH) under conditions of a pressure of 10 MPa, a temperature of 250 ° C. and a time of 30 minutes. In order to carry out in a nitrogen atmosphere, it was carried out using a body frame manufactured by Tanken Seal Seiko Co., Ltd. while passing 0.5 liters of nitrogen per minute. After cooling once, heat treatment was then performed under no pressure, at a temperature of 420 ° C. for 60 minutes. This heat treatment was performed using a general tube-type heating furnace with nitrogen flowing at 0.5 liters per minute in order to perform in a nitrogen atmosphere. In addition, since it is not the composite ribbon which formed the resin layer, it does not adhere | attach but is not a laminated body. Measurement was performed with five thin ribbons stacked. The results are shown in Table 2. The relative magnetic permeability was as high as 15,120, and the core loss was as low as 9.8 W / kg, confirming that the Co-based amorphous alloy ribbon has excellent magnetic properties. However, the obtained ribbon was very brittle and could be broken unless handled carefully, and the tensile strength could not be measured.
[0043]
[Example 8]
The composite ribbon shown in the synthesis example was punched into a ring shape for measuring relative permeability and core loss, and a JIS standard test piece for measuring tensile strength. 5 pieces of ring-shaped ones and 20 pieces of test piece-like ones are stacked in the same direction, and using a heat press machine (TOYOSEIKI mini test press type WCH) under the conditions of pressure 10 MPa, temperature 250 ° C., time 30 minutes. Lamination was performed to obtain a laminate. In order to carry out in a nitrogen atmosphere, it was carried out using a body frame manufactured by Tanken Seal Seiko Co., Ltd. while passing 0.5 liters of nitrogen per minute. After cooling once, heat treatment was then performed under no pressure, at a temperature of 420 ° C., for 60 minutes. This heat treatment was performed using a general tube-type heating furnace with nitrogen flowing at 0.5 liters per minute in order to perform in a nitrogen atmosphere. When the magnetic properties were measured, the relative permeability was 14,780 and the core loss was 9.9 W / kg, and it had the same level of performance as the magnetic properties of only the amorphous alloy ribbon processed under the same conditions. It was. The tensile strength was 102 MPa and the mechanical strength was excellent. The results are shown in Table 2.
[0044]
Examples 9 to 13
In the same manner as in Example 8, lamination adhesion was performed under the conditions shown in Table 2, followed by annealing, and evaluation was performed. The results are shown in Table 2.
[0045]
[Comparative Examples 7 to 11]
In the same manner as in Example 8, lamination adhesion was performed under the conditions shown in Table 2, followed by annealing, and evaluation was performed. The results are shown in Table 2.
[0046]
[Table 1]
[Table 2]
【The invention's effect】
The amorphous alloy ribbon laminated body of the present invention is a material having both excellent magnetic properties and mechanical strength inherent to Co-based amorphous alloy ribbons, and has performance that could not be achieved by the prior art. Material. The amorphous alloy ribbon laminate of the present invention uses a Co-based amorphous alloy ribbon as an amorphous alloy ribbon, and is laminated and bonded under specific pressure, temperature, and time conditions. It can be manufactured by laminating and bonding under conditions of pressure, temperature and time, and then annealing under conditions of specific pressure, temperature and time. The amorphous alloy ribbon laminate of the present invention can be suitably used as a magnetic application part including the amorphous alloy, and specifically includes, for example, an inductance, various coils, various transformers, a noise filter, and a magnetic sensor. It can be suitably used for magnetic heads, antennas, radio wave absorbers, motors, various cores, and wiring boards.
Claims (6)
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| JP2002274132A JP4183463B2 (en) | 2002-09-19 | 2002-09-19 | Amorphous alloy ribbon laminate and method for producing the same |
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| JP2002274132A JP4183463B2 (en) | 2002-09-19 | 2002-09-19 | Amorphous alloy ribbon laminate and method for producing the same |
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| Publication Number | Publication Date |
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| JP2004106426A JP2004106426A (en) | 2004-04-08 |
| JP4183463B2 true JP4183463B2 (en) | 2008-11-19 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8137409B2 (en) | 2000-06-23 | 2012-03-20 | University College London | Method of installing a transcutaneous prosthesis |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8137409B2 (en) | 2000-06-23 | 2012-03-20 | University College London | Method of installing a transcutaneous prosthesis |
| US8628584B2 (en) | 2000-06-23 | 2014-01-14 | University College London | Transcutaneous prosthesis |
| US9452066B2 (en) | 2000-06-23 | 2016-09-27 | University College London | Transcutaneous prosthesis |
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| JP2004106426A (en) | 2004-04-08 |
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