WO2014091633A1

WO2014091633A1 - Electrode material for thermal fuse and production method therefor

Info

Publication number: WO2014091633A1
Application number: PCT/JP2012/082580
Authority: WO
Inventors: 英生汲田; 慎也眞々田; 真弘山口
Original assignee: 株式会社徳力本店
Priority date: 2012-12-14
Filing date: 2012-12-14
Publication date: 2014-06-19
Also published as: JP6021284B2; JPWO2014091633A1

Abstract

The present invention relates to an electrode material for a thermal fuse that uses a cladding material formed by bonding two or more metal materials having differing properties and a production method for the electrode material. The electrode material for a thermal fuse is configured so as to comprise a multilayer structure that is achieved by performing an internal oxidation treatment on an alloy containing 1-50 mass% of Cu and a remainder of Ag and unavoidable impurities or on an alloy comprising 1-50 mass% of Cu, 0.01-5 mass% of at least one of the elements selected from the group consisting of Sn, In, Ti, Fe, Ni, and Co, and a remainder of Ag and unavoidable impurities in order to form an internally oxidized layer on the surface of both the front and rear surfaces of the material. The resulting multilayer structure has a substrate layer in the central section of the material thereof and, as necessary, a bonding layer on both surfaces of the substrate layer.

Description

温度ヒューズ用電極材料およびその製造方法Electrode material for thermal fuse and method for manufacturing the same

　本発明は、電子機器や家電用電気製品において、それらの機器が異常高温となるのを防止するために取り付ける温度ヒューズ用の電極材料およびその製造方法に関する。 [Technical Field] The present invention relates to an electrode material for a thermal fuse to be mounted to prevent an abnormally high temperature of an electronic device or an electric appliance for home appliances, and a method for manufacturing the same.

　電子機器や電気機器が異常高温となるのを防止するために取り付ける温度ヒューズは、感温ペレットが動作温度で溶融して強圧縮ばねの発力を除荷し、強圧縮ばねが伸長することにより、その強圧縮ばねにより圧接されていた電極材料とリード線とが離隔して電流を遮断するものである。 Thermal fuses that are installed to prevent electronic and electrical equipment from becoming extremely hot are because the temperature-sensitive pellet melts at the operating temperature, unloads the force of the strong compression spring, and the strong compression spring extends. The electrode material pressed by the strong compression spring is separated from the lead wire to cut off the current.

　この温度ヒューズに用いる電極材料としては、Ａｇ－酸化物合金が主流となりつつある(例えば、特許文献１、特許文献２)。 As an electrode material used for this thermal fuse, an Ag-oxide alloy is becoming mainstream (for example, Patent Document 1 and Patent Document 2).

　電極材料は、温度ヒューズの機構上、０．１ｍｍ以下の薄板が用いられるもので、リード線との接触面が長時間にわたって通電状態のまま保持されるために、リード線もしくは金属ケースとの溶着現象を引き起こしやすく、材料特性として耐溶着性が求められる。さらに近時では、Ａｇ－酸化物合金の材料価格低減も求められている。 The electrode material is a thin plate of 0.1 mm or less due to the thermal fuse mechanism, and the contact surface with the lead wire is kept energized for a long time, so it is welded to the lead wire or metal case. Phenomenon easily occurs, and welding resistance is required as a material property. In recent years, there has been a demand for a reduction in the material price of Ag-oxide alloys.

　この耐溶着性および材料価格低減の要求に対しては、Ａｇ－酸化物合金中の酸化物の含有量を増やし、Ａｇの含有量を減少させることによって対応することが可能である。 The demand for welding resistance and material cost reduction can be met by increasing the oxide content in the Ag-oxide alloy and decreasing the Ag content.

　しかしながら、Ａｇ－酸化物合金は、酸化物の増加に伴い、圧延加工性が著しく低下し、内部酸化後の圧延工程において薄板に加工することが困難となる。 However, the Ag-oxide alloy has a marked decrease in rolling processability with the increase in oxide, making it difficult to process into a thin plate in the rolling process after internal oxidation.

特開平１０－１６２７０４号公報Japanese Patent Laid-Open No. 10-162704 特許第４３８３８５９号公報Japanese Patent No. 4383859

　近時、温度ヒューズ用電極材料に求められる耐溶着性、低い接触抵抗および加工性等の諸特性を維持しつつ、より一層の材料価格低減を目的として、高価な貴金属であるＡｇの含有量をさらに減少させることが求められている。 Recently, the content of Ag, which is an expensive noble metal, has been reduced for the purpose of further reducing the material price while maintaining various characteristics such as welding resistance, low contact resistance and workability required for electrode materials for thermal fuses. Further reduction is required.

　しかしながら、従来の製造方法では、Ａｇ－Ｃｕ合金中のＣｕの含有量が５０質量％に近づくにつれて酸化物含有量が増加するのに伴い、接触抵抗が上昇し、導電性が悪化することにより温度上昇を招き、温度ヒューズ用の電極材料には適さなくなる。このため、Ａｇ－Ｃｕ合金中のＡｇの含有量を減少させることによるこれ以上の材料価格低減が困難であった。 However, in the conventional manufacturing method, as the Cu content in the Ag-Cu alloy approaches 50 mass%, the contact resistance increases and the conductivity deteriorates as the oxide content increases. It rises and becomes unsuitable for electrode materials for thermal fuses. For this reason, it has been difficult to further reduce the material price by reducing the Ag content in the Ag—Cu alloy.

　また、内部酸化物層は酸化物を含んで硬いため、圧延加工性が乏しくなり、圧延加工性を向上させるには、酸化物含有量を減少させる必要があった。 Also, since the internal oxide layer is hard to contain oxides, the rolling processability is poor, and it was necessary to reduce the oxide content in order to improve the rolling processability.

　本発明は、このような問題を解決することを課題とする。 This invention makes it a subject to solve such a problem.

　そこで本発明は、ＣｕもしくはＣｕ合金からなる基板の長手方向の表裏両面にＡｇ－Ｃｕ合金板をクラッド加工することにより、基板層とＡｇ－Ｃｕ合金層とを形成し、これに内部酸化処理を施すことで前記Ａｇ－Ｃｕ合金層の表層に内部酸化層を形成した多層構造を有する温度ヒューズ用電極材料とするものである。また、接合強度をさらに向上させたい場合には、上記基板層および上記Ａｇ－Ｃｕ合金層の界面において、接合強度を向上させることができる接合層を必要に応じて設けても良い。 Therefore, the present invention forms a substrate layer and an Ag—Cu alloy layer by clad an Ag—Cu alloy plate on both front and back surfaces in the longitudinal direction of the substrate made of Cu or Cu alloy, and performs internal oxidation treatment on this. By applying this, an electrode material for a thermal fuse having a multilayer structure in which an internal oxide layer is formed on the surface layer of the Ag—Cu alloy layer is obtained. In order to further improve the bonding strength, a bonding layer capable of improving the bonding strength may be provided as necessary at the interface between the substrate layer and the Ag—Cu alloy layer.

　上記のような多層構造を有する温度ヒューズ用電極材料は、材料の大部分を占める安価な上記基板層がＡｇを含まない為、従来の製造方法に比べてより一層の材料価格低減を可能とし、さらに上記基板層が加工性に富んでいるため、内部酸化層中の酸化物含有量は維持しつつ、内部酸化後の材料を圧延加工する際の加工性を向上させることに成功した。 The thermal fuse electrode material having a multilayer structure as described above allows the material cost to be further reduced as compared with the conventional manufacturing method because the inexpensive substrate layer that occupies most of the material does not contain Ag. Further, since the substrate layer is rich in workability, it has succeeded in improving workability when rolling the material after internal oxidation while maintaining the oxide content in the internal oxide layer.

　各層の組成として、上記基板層おいては、不可避不純物を含む純Ｃｕが好ましいが、耐熱性、導電性もしくは機械的性質を向上させる目的で、Ｔｉ、Ｃｒ、Ｂｅ、Ｓｉ、Ｆｅ、Ｃｏ、Ｚｒ、Ｚｎ、Ｓｎ、Ｎｉ、Ｐ、Ｐｂの少なくとも１種を含むＣｕ合金を用いても良い。 As the composition of each layer, pure Cu containing inevitable impurities is preferable in the substrate layer, but for the purpose of improving heat resistance, conductivity or mechanical properties, Ti, Cr, Be, Si, Fe, Co, Zr Cu alloy containing at least one of Zn, Sn, Ni, P, and Pb may be used.

　上記Ａｇ－Ｃｕ合金板は、Ｃｕを１～５０質量％含み、かつ残部がＡｇおよび不可避不純物を含む合金、もしくはＣｕを１～５０質量％含み、さらにＳｎ、Ｉｎ、Ｔｉ、Ｆｅ、ＮｉおよびＣｏの群から選ばれた少なくとも１種を０．０１～５質量％含み、かつ残部がＡｇおよび不可避不純物を含む合金が好ましい。 The Ag—Cu alloy plate contains 1 to 50% by mass of Cu and the balance contains Ag and inevitable impurities, or contains 1 to 50% by mass of Cu, and further includes Sn, In, Ti, Fe, Ni and Co. An alloy containing 0.01 to 5% by mass of at least one selected from the group consisting of Ag and inevitable impurities is preferred.

　ここで、Ａｇ－Ｃｕ合金板中のＣｕの添加量を１～５０質量％とした理由は、内部酸化処理後において、Ｃｕの含有量が１質量％未満では、酸化物が不足し、温度ヒューズ用電極材料として使用するのに十分な耐溶着性が得られないためである。つまり内部酸化層とは、酸化物の含有量が１質量％以上の層のことをいう。Ｃｕの含有量が５０質量％を超えると、酸化物含有量の増加よって内部酸化層の加工性が著しく低下し、内部酸化層に割れが生じやすくなる。さらに、内部酸化処理により酸素をＡｇ－Ｃｕ合金板中に侵入させようとしても、酸素が主にＣｕと結合して表面付近で酸化皮膜を形成してしまい、酸化物粒子をＡｇマトリックス中に分散させて生じさせることが難しくなる。 Here, the reason for the addition amount of Cu in the Ag—Cu alloy sheet being 1 to 50 mass% is that, after the internal oxidation treatment, if the Cu content is less than 1 mass%, the oxide is insufficient, and the temperature fuse This is because sufficient welding resistance to be used as an electrode material for a battery cannot be obtained. That is, the internal oxide layer refers to a layer having an oxide content of 1% by mass or more. When the Cu content exceeds 50% by mass, the workability of the internal oxide layer is remarkably reduced due to the increase in the oxide content, and the internal oxide layer is easily cracked. Furthermore, even if oxygen is allowed to penetrate into the Ag-Cu alloy plate by internal oxidation treatment, oxygen mainly binds to Cu to form an oxide film near the surface, and the oxide particles are dispersed in the Ag matrix. Making it difficult to generate.

　上記接合層として挙げられるものとしては、不可避不純物を含む純Ａｇ、もしくはＣｕを０．０１～２８重量％含み、かつ残部がＡｇおよび不可避不純物を含む組成からなる合金等が最も好ましいが、上記Ａｇ－Ｃｕ合金板、Ａｕ等の貴金属、Ｍｇ、Ｃｒ、Ｓｎ、Ｉｎ、Ｔｉ、Ｆｅ、ＮｉもしくはＣｏ等、適度な接合性を有していればどのような金属材料でも良い。 As the bonding layer, pure Ag containing inevitable impurities or an alloy having a composition containing 0.01 to 28% by weight of Cu and the balance containing Ag and inevitable impurities is most preferable. Any metal material may be used as long as it has appropriate bonding properties, such as a Cu alloy plate, a noble metal such as Au, Mg, Cr, Sn, In, Ti, Fe, Ni, or Co.

　この接合層は、基板層とＡｇ－Ｃｕ合金層との接合性を向上させるものであり、加工時の伸び率の違い、振動もしくは衝撃により剥離するのを防止するものである。接合性をさらに向上させる場合には、基板層、接合層およびＡｇ－Ｃｕ合金層の少なくとも１層において、熱処理により構成成分の一部を隣接する他の層へ拡散もしくは合金化させても良い。さらに、この接合層は、内部酸化処理時において接合層の表層に内部酸化処理が施され、隣接する基板層に内部酸化処理が施される直前まで、酸素が基板層へ侵入してＣｕが酸化することによって生じうる内部酸化層の剥離を防止する機能も有する。 This bonding layer improves the bondability between the substrate layer and the Ag—Cu alloy layer, and prevents peeling due to differences in elongation during processing, vibration or impact. In order to further improve the bonding property, in at least one of the substrate layer, the bonding layer, and the Ag—Cu alloy layer, a part of the constituent components may be diffused or alloyed to other adjacent layers by heat treatment. Further, this bonding layer is subjected to an internal oxidation process on the surface layer of the bonding layer during the internal oxidation process, and oxygen enters the substrate layer and Cu is oxidized until immediately before the adjacent substrate layer is subjected to the internal oxidation process. It also has a function of preventing peeling of the internal oxide layer that may be caused by this.

　ここで、接合層の上記合金中に含まれるＣｕの添加量を０．０１～２８質量％とした理由は、Ｃｕの含有量が２８質量％を超えると、隣接する板材との接合性が好ましくないためである。なお、内部酸化条件にもよるが、Ｃｕの含有量が２８質量％を超えた接合層は、Ｃｕの含有量が２８質量％以下の接合層に比べて、内部酸化処理時において酸素が基板層へ侵入してＣｕが酸化することによって生じうる内部酸化層の剥離を防止する機能が高い。 Here, the reason why the added amount of Cu contained in the alloy of the bonding layer is 0.01 to 28% by mass is that when the Cu content exceeds 28% by mass, the bonding property to the adjacent plate material is preferable. This is because there is not. Although depending on the internal oxidation conditions, the bonding layer in which the Cu content exceeds 28% by mass is more oxygenated during the internal oxidation treatment than the bonding layer in which the Cu content is 28% by mass or less. It has a high function of preventing peeling of the internal oxide layer that may be caused by Cu entering and oxidizing Cu.

　上記本発明に係る温度ヒューズ用電極材料の製造方法としては、クラッド法が最も好ましい。クラッド法は、上記各種層となる板材を電流加熱した後に、基板層となる板材に対して、Ａｇ－Ｃｕ合金層もしくは接合層を構成する板材を被せ、熱間圧延加工により接合し、複数の前記各種層からなる多層構造材を形成する方法である。その後、上記多層構造材に内部酸化処理を施すことにより、多層構造材の表裏両面のＡｇ－Ｃｕ合金層の表層に内部酸化層を形成する。 The clad method is the most preferable method for producing the thermal fuse electrode material according to the present invention. In the clad method, after the plate materials to be various layers are subjected to current heating, the plate material to be the substrate layer is covered with a plate material constituting an Ag—Cu alloy layer or a bonding layer, and is joined by hot rolling, This is a method of forming a multilayer structure material composed of the various layers. Thereafter, by subjecting the multilayer structure material to internal oxidation treatment, an internal oxide layer is formed on the surface layer of the Ag—Cu alloy layer on both the front and back surfaces of the multilayer structure material.

　多層構造材の他の製造方法としては、めっき法もしくはスパッタリング法が好ましい。めっき法は、Ａｇ－Ｃｕ合金層もしくは接合層を構成する金属塩を含むめっき液を用いて、基板層上に電解または無電解でめっきを行う方法である。スパッタリング法は、Ａｇ－Ｃｕ合金層もしくは接合層を構成するターゲット材、必要に応じて酸素性雰囲気を用いて、基板層上に薄膜を形成するものである。 As another method for producing a multilayer structure material, a plating method or a sputtering method is preferable. The plating method is a method of performing electrolysis or electroless plating on a substrate layer using a plating solution containing a metal salt constituting an Ag—Cu alloy layer or a bonding layer. In the sputtering method, a thin film is formed on a substrate layer using a target material constituting an Ag—Cu alloy layer or a bonding layer and, if necessary, an oxygen atmosphere.

　なお、さらに多層構造材の他の製造方法として挙げられるものは、プラズマ溶射、ガス溶射、高速フレーム溶射、コールドスプレー法等の溶射での積層、空中や液中での断続的な放電、パルス等の放電による積層およびＰＶＤ（Ｐｈｙｓｉｃａｌ　Ｖａｐｏｒ　Ｄｅｐｏｓｉｔｉｏｎ）、ＣＶＤ（Ｃｅｍｉｃａｌ　Ｖａｐｏｒ　Ｄｅｐｏｓｉｔｉｏｎ）等の蒸着法による積層等がある。 Further, other examples of the manufacturing method of the multilayer structure material include plasma spraying, gas spraying, high-speed flame spraying, laminating by spraying such as a cold spray method, intermittent discharge in the air or liquid, pulse, etc. There are a stacking by a discharge and a stacking by a vapor deposition method such as PVD (Physical Vapor Deposition) and CVD (Chemical Vapor Deposition).

　本発明に係る温度ヒューズ用電極材料の製造方法は、上記製造方法を組み合わせた方法でもよく、例えば、基板層を材料中央部として、片方の面はクラッド法、反対側の面はメッキ法という具合でもよい。 The manufacturing method of the thermal fuse electrode material according to the present invention may be a method combining the above manufacturing methods. For example, the substrate layer is the material central portion, one surface is a cladding method, and the opposite surface is a plating method. But you can.

　さらに、基板層を材料中央部として、表裏非対称の上記各種層および／もしくは内部酸化層を配置してもよい。例えば、片方の面の表層は内部酸化層、反対側の面の表層は接合層もしくはＡｇ－Ｃｕ合金層という具合でもよい。 Furthermore, the above-mentioned various layers and / or internal oxide layers that are asymmetrical on the front and back sides may be arranged with the substrate layer as the center of the material. For example, the surface layer on one side may be an internal oxide layer, and the surface layer on the opposite side may be a bonding layer or an Ag—Cu alloy layer.

　内部酸化処理は、Ａｇ－Ｃｕ合金層において、Ａｇ中にあらかじめ含有されたＣｕが、材料表層からＡｇ中に吸蔵される酸素と結び付くことにより、Ａｇマトリックス中に酸化物として析出するという過程をとる。このとき、溶質元素であるＣｕは、上記Ａｇ－Ｃｕ合金層の材料内部から表層に向かって拡散する現象が生じる。なお、本発明で言う表層の定義とは、材料表面からＡｇ－Ｃｕ合金層および接合層の総厚以下の範囲のことを言う。 The internal oxidation treatment takes a process in which, in the Ag—Cu alloy layer, Cu previously contained in Ag is precipitated as an oxide in the Ag matrix by being combined with oxygen stored in Ag from the material surface layer. . At this time, Cu, which is a solute element, diffuses from the material inside the Ag—Cu alloy layer toward the surface layer. Note that the definition of the surface layer in the present invention refers to a range not more than the total thickness of the Ag—Cu alloy layer and the bonding layer from the material surface.

　溶質元素が材料内部から表層に向かって拡散する現象は、上記Ａｇ－Ｃｕ合金層の材料表面から内部に向かって析出した酸化物で形成される内部酸化層と、時間の経過により析出が起きていない未酸化層との間でＣｕの濃度に差が生じ、その濃度勾配を埋めるために未酸化層から表層に向かいＣｕが拡散する現象である。この為、常にＡｇマトリックス中の他元素の酸化に必要な酸素量を上回る酸素を供給して行う。 The phenomenon that the solute element diffuses from the inside of the material toward the surface layer is caused by the internal oxide layer formed by the oxide precipitated from the material surface of the Ag—Cu alloy layer toward the inside, and the precipitation over time. This is a phenomenon in which a difference in Cu concentration occurs between the unoxidized layer and the non-oxidized layer, and Cu diffuses from the unoxidized layer toward the surface layer in order to fill the concentration gradient. For this reason, oxygen is always supplied in excess of the amount of oxygen necessary for the oxidation of other elements in the Ag matrix.

　上記拡散の過程において、上記Ａｇ－Ｃｕ合金層中にＳｎ、Ｉｎ、Ｔｉ、Ｆｅ、Ｎｉ、およびＣｏの群から選ばれた少なくとも１種を加えることにより、濃度勾配による拡散現象を抑制し、その結果、析出する酸化物の移動による凝集を抑制することで酸化組織を微細にし、均質な分散が得られる。さらに、Ｃｕとの複合酸化物、例えば（Ｃｕ－Ｓｎ）Ｏｘとなり、耐溶着性を向上させる効果がある。 In the diffusion process, by adding at least one selected from the group consisting of Sn, In, Ti, Fe, Ni, and Co into the Ag—Cu alloy layer, the diffusion phenomenon due to the concentration gradient is suppressed, As a result, by suppressing the aggregation due to the movement of the deposited oxide, the oxide structure is made finer and a uniform dispersion can be obtained. Furthermore, it becomes a complex oxide with Cu, for example, (Cu—Sn) Ox, and has the effect of improving the welding resistance.

　ここで、上記Ａｇ－Ｃｕ合金層において、Ｓｎ、Ｉｎ、Ｔｉ、Ｆｅ、ＮｉもしくはＣｏの少なくとも１種を０．０１～５質量％とした理由は、０．０１質量％より少ないと内部酸化処理時の溶質元素の移動を十分に抑制できず、酸化物の均質な分散が得られないためであり、５質量％を超えると結晶粒界などに粗い酸化物を形成し、接触抵抗の上昇を招くためである。 Here, in the Ag—Cu alloy layer, at least one of Sn, In, Ti, Fe, Ni or Co is made 0.01 to 5% by mass. This is because the movement of the solute element at the time cannot be sufficiently suppressed, and a homogeneous dispersion of the oxide cannot be obtained. When the amount exceeds 5 mass%, a coarse oxide is formed at the grain boundary and the contact resistance is increased. This is to invite.

　本発明は、この内部酸化処理において、材料表裏両面の表層だけが内部酸化組織となるようにすることを特徴とし、そのための内部酸化条件を、所望の板厚にて内部酸化炉中で５００℃～７５０℃、０．２５時間以上、酸素分圧０．１～２ＭＰａの条件で調整している。これによって材料表裏両面の表層に内部酸化層、材料中心部に基板層を形成することができる。内部酸化層に分散する酸化物粒子の平均粒径は０．５～５μｍであり、好ましくは１～４μｍであり、より好ましくは２～３μｍである。酸化物粒子の平均粒径が０．５μｍ未満ではリード線と可動電極との接触部において酸化物粒子の粒径が微細なため、溶着しやすくなり、一方、酸化物粒子の平均粒径が５μｍより大きいと、接触抵抗が高くなるため、溶着しやすくなる。 The present invention is characterized in that, in this internal oxidation treatment, only the surface layers on both the front and back surfaces of the material have an internal oxide structure, and the internal oxidation conditions for this are set at 500 ° C. in an internal oxidation furnace at a desired plate thickness. It is adjusted under the conditions of ˜750 ° C., 0.25 hours or more, and oxygen partial pressure of 0.1 to 2 MPa. As a result, an internal oxide layer can be formed on the front and back surfaces of the material, and a substrate layer can be formed at the center of the material. The average particle size of the oxide particles dispersed in the internal oxide layer is 0.5 to 5 μm, preferably 1 to 4 μm, more preferably 2 to 3 μm. When the average particle size of the oxide particles is less than 0.5 μm, the oxide particles are fine at the contact portion between the lead wire and the movable electrode, so that the oxide particles are easily welded. On the other hand, the average particle size of the oxide particles is 5 μm. If it is larger, the contact resistance becomes higher, so that welding becomes easier.

　内部酸化処理時の酸素分圧は、酸化物粒子の平均粒径を０．５～５μｍに調整する上で重要である。内部酸化条件の内部酸化処理時の酸素分圧は０．１～２ＭＰａが好ましい。すなわち、酸素分圧が０．１ＭＰａ未満であると内部酸化層を均一に形成することが難しく、酸化物粒子の平均粒径が５μｍより大きくなり、酸素分圧が２ＭＰａより大きいと酸化物粒子の平均粒径が０．５μｍ未満となって前述のように溶着しやすくなる。 The oxygen partial pressure during the internal oxidation treatment is important for adjusting the average particle size of the oxide particles to 0.5 to 5 μm. The oxygen partial pressure during the internal oxidation treatment under internal oxidation conditions is preferably 0.1 to 2 MPa. That is, when the oxygen partial pressure is less than 0.1 MPa, it is difficult to form the internal oxide layer uniformly, the average particle size of the oxide particles is greater than 5 μm, and when the oxygen partial pressure is greater than 2 MPa, The average particle size becomes less than 0.5 μm, and it becomes easy to weld as described above.

　内部酸化処理時の温度は上記の如く、５００℃～７５０℃が好ましい。５００℃より低温であると十分に酸化反応が進まず、一方、７５０℃より高温であると、内部酸化層の厚さや酸化物粒子の大きさを制御しにくくなる。 The temperature during the internal oxidation treatment is preferably 500 ° C. to 750 ° C. as described above. When the temperature is lower than 500 ° C., the oxidation reaction does not proceed sufficiently. On the other hand, when the temperature is higher than 750 ° C., it becomes difficult to control the thickness of the internal oxide layer and the size of the oxide particles.

　内部酸化処理の時間は、目的とする内部酸化層の層厚、未酸化層の層厚、Ａｇ－Ｃｕ合金板の組成、接合層およびＡｇ－Ｃｕ合金層の層厚、前述した内部酸化時の温度および酸素分圧により適宜調整する必要がある。 The time of the internal oxidation treatment is the layer thickness of the target internal oxide layer, the layer thickness of the unoxidized layer, the composition of the Ag—Cu alloy plate, the layer thickness of the bonding layer and the Ag—Cu alloy layer, It is necessary to adjust appropriately according to temperature and oxygen partial pressure.

　目的とする内部酸化層の層厚にもよるが、０．２５時間以上が好ましい。すなわち、内部酸化時間が０．２５時間未満であると内部酸化層を均一に形成することが難しい。内部酸化時間が０．２５時間未満であると、内部酸化層を均一かつ十分に形成することが難しく、温度ヒューズ用電極材料として用いた際にリード線もしくは金属ケースとの溶着現象を起こす恐れがある。内部酸化時間には特に上限は無く、内部酸化時間の増大に比例して内部酸化層の層厚が厚くなる。しかし、基板層が内部酸化されると各層の剥離の原因となる為、基板層に内部酸化処理が施されないように、基板層に対するＡｇ－Ｃｕ合金層もしくは接合層の層厚の比率を高めるか、多層構造材の板厚が厚い状態で内部酸化処理を入れる必要がある。あるいは、基板層との界面に酸化を防止する層を設けても良い。 Although it depends on the thickness of the target internal oxide layer, it is preferably 0.25 hours or longer. That is, when the internal oxidation time is less than 0.25 hours, it is difficult to form the internal oxide layer uniformly. If the internal oxidation time is less than 0.25 hours, it is difficult to form the internal oxide layer uniformly and sufficiently, and there is a risk of causing a welding phenomenon with the lead wire or the metal case when used as an electrode material for a thermal fuse. is there. There is no particular upper limit to the internal oxidation time, and the thickness of the internal oxide layer increases in proportion to the increase in internal oxidation time. However, if the substrate layer is internally oxidized, it may cause peeling of each layer, so that the ratio of the thickness of the Ag—Cu alloy layer or the bonding layer to the substrate layer should be increased so that the substrate layer is not subjected to internal oxidation treatment. In addition, it is necessary to insert an internal oxidation treatment in a state where the multilayer structure material is thick. Alternatively, a layer for preventing oxidation may be provided at the interface with the substrate layer.

　なお、内部酸化の温度、圧力、時間にはそれぞれ相関関係があり、例えば内部酸化時間を短時間で行うには、温度と圧力を高くして調整するなど、内部酸化処理を施す材料によってそれぞれ最適な条件を選択する必要がある。 In addition, the temperature, pressure, and time of internal oxidation are correlated with each other. For example, in order to shorten the internal oxidation time in a short time, the temperature and pressure are increased and adjusted. It is necessary to select a proper condition.

　温度ヒューズ用電極材料は、温度ヒューズ使用用途により種々の成分組成や各種最終板厚があるが、温度ヒューズの機構上０．１ｍｍ以下の薄板材が用いられる。しかし、薄板材に内部酸化処理を均一に行うことが難しく、薄板材を均一にクラッド加工することが困難であるため、クラッド加工後の材料を圧延加工により薄板化する必要がある。なお、内部酸化後の材料において、加工性が悪く、圧延加工時の割れおよび破断と内部酸化層の割れ等が生じる場合には、せん断加工もしくは熱処理を必要に応じて施しても良い。 The electrode material for the thermal fuse has various component compositions and various final plate thicknesses depending on the usage of the thermal fuse, but a thin plate material of 0.1 mm or less is used due to the mechanism of the thermal fuse. However, since it is difficult to uniformly perform the internal oxidation treatment on the thin plate material and it is difficult to uniformly clad the thin plate material, it is necessary to thin the material after the clad processing by rolling. In addition, in the material after internal oxidation, when workability is poor and cracks and breaks during rolling, cracks in the internal oxide layer, and the like occur, shearing or heat treatment may be performed as necessary.

　本発明の内部酸化後の圧延工程および焼鈍工程における従来の製造方法との相違点として、温度ヒューズ用電極材料中心部に加工性に富んだＣｕもしくはＣｕ合金からなる基板層を設けたことにより、内部酸化層の酸化物含有量を減らすことなく圧延加工性を大幅に向上させることが可能であり、断面減少率で８０％以上の圧延加工をすることに成功した。さらに、加工性に富んだ基板層を設けたことにより、単層では比較的加工性に劣るその他の各種層の加工性を向上させることが可能となるため、各々の層を形成するクラッド加工時の板材の比率および多層構造を保ったまま、０．１ｍｍ以下の薄板材に圧延加工することに成功した。 As a difference from the conventional manufacturing method in the rolling process and annealing process after internal oxidation of the present invention, by providing a substrate layer made of Cu or Cu alloy with high workability at the center part of the electrode material for the thermal fuse, It was possible to greatly improve the rolling processability without reducing the oxide content of the internal oxide layer, and succeeded in rolling with a reduction rate of 80% or more in cross-section reduction rate. Furthermore, by providing a workable substrate layer, it is possible to improve the workability of various other layers that are relatively inferior with a single layer. The sheet material was successfully rolled to a thin sheet material of 0.1 mm or less while maintaining the ratio and the multilayer structure.

　本発明の電極材料によると、Ａｇ－Ｃｕ合金層のＣｕの含有量を５０質量％まで増加させて、内部酸化処理後の酸化物含有量を増やすことによりＡｇの含有量を減少させても、内部酸化後の加工において、断面減少率で８０％以上の圧延加工が可能となる。 According to the electrode material of the present invention, even if the content of Ag is decreased by increasing the Cu content in the Ag-Cu alloy layer to 50 mass% and increasing the oxide content after the internal oxidation treatment, In the processing after the internal oxidation, it is possible to perform a rolling process with a cross-section reduction rate of 80% or more.

　つまり、従来の温度ヒューズ用電極材料に比べ、電極材料の表裏両面に十分な層厚の内部酸化層を有し、かつ材料中心部にＣｕを主成分とする基板層を設けたことにより、内部酸化層の酸化物含有量を減らすことなく加工性を大きく向上させることが可能である。これにより、安定した品質かつ信頼性が高い温度ヒューズ用電極材料を提供することが可能になる。加えて、材料中心部の基板の材質を任意に変更することで、耐溶着性を維持しつつ、耐熱性、導電性もしくは機械的性質等を所望の諸特性に調整した温度ヒューズ用電極材料を提供することが可能になる。 In other words, compared to conventional electrode materials for thermal fuses, the internal oxide layer having a sufficient thickness on both the front and back surfaces of the electrode material and a substrate layer mainly composed of Cu at the center of the material are provided. Workability can be greatly improved without reducing the oxide content of the oxide layer. As a result, it is possible to provide a temperature fuse electrode material having stable quality and high reliability. In addition, by arbitrarily changing the material of the substrate at the center of the material, an electrode material for thermal fuse that adjusts heat resistance, conductivity, mechanical properties, etc. to desired characteristics while maintaining welding resistance It becomes possible to provide.

　さらに温度ヒューズ用電極材料に求められる耐溶着性、低い接触抵抗等の諸特性を維持しつつ、Ａｇ等の使用量を大幅に削減することができ、安価な温度ヒューズ用電極材料を提供することが可能となる。 Furthermore, it is possible to provide an inexpensive thermal fuse electrode material that can greatly reduce the amount of Ag and the like while maintaining various characteristics such as welding resistance and low contact resistance required for the thermal fuse electrode material. Is possible.

製造方法１および製造方法３における３層クラッド板の長手方向断面を示す説明図Explanatory drawing which shows the longitudinal direction cross section of the 3 layer clad board in the manufacturing method 1 and the manufacturing method 3 製造方法１および製造方法３における内部酸化処理後の３層クラッド板の長手方向断面を示す説明図Explanatory drawing which shows the longitudinal direction cross section of the 3 layer clad board after the internal oxidation process in the manufacturing method 1 and the manufacturing method 3 製造方法２および製造方法４における３層クラッド板の長手方向断面を示す説明図Explanatory drawing which shows the longitudinal direction cross section of the 3 layer clad board in the manufacturing method 2 and the manufacturing method 4 製造方法２および製造方法４における５層クラッド板の長手方向断面を示す説明図Explanatory drawing which shows the longitudinal direction cross section of the 5-layer clad board in the manufacturing method 2 and the manufacturing method 4 製造方法２および製造方法４における内部酸化処理後の５層クラッド板の長手方向断面を示す説明図Explanatory drawing which shows the longitudinal direction cross section of the 5-layer clad board after the internal oxidation process in the manufacturing method 2 and the manufacturing method 4 比較例におけるＡｇ－酸化物合金板の長手方向断面を示す説明図Explanatory drawing which shows the longitudinal direction cross section of the Ag-oxide alloy board in a comparative example

　本発明の実施例を表１～４に示し、これらの温度ヒューズ用電極材料の製造方法を説明する。なお、実施例および比較例は電極材料種類Ｎｏ．で区別し、表１に対応する形式で表２を、表３に対応する形式で表４を示す。 Examples of the present invention are shown in Tables 1 to 4, and a method for manufacturing these thermal fuse electrode materials will be described. In addition, an Example and a comparative example are electrode material kind No .. Table 2 is shown in a format corresponding to Table 1, and Table 4 is shown in a format corresponding to Table 3.

　具体的には、本発明の製造方法１～２のＡｇ－Ｃｕ合金板および接合板に含まれる成分組成を表１に、本発明の製造方法３～４のＡｇ－Ｃｕ合金板および接合板に含まれる成分組成を表３に記載する。また、比較例のＡｇ－Ｃｕ合金板に含まれる成分組成を表１および表３に併記する。表１もしくは表３に対応する形で、内部酸化温度、内部酸化時間、酸素分圧、酸化物の平均粒径、内部酸化処理後およびクラッド加工後の圧延加工の加工性、温度ヒューズ用電極材料の最終板厚および最終加工率を表２もしくは表４に記載する。表１～４に記載の各項目の評価方法として、Ａｇ－Ｃｕ合金板および接合板に含まれる成分組成は、波長分散型電子顕微鏡およびＩＣＰ発光分析装置を用いて定量分析を行い、成分組成の残部であるＡｇおよび不可避不純物は残と記載した。なお、本発明の実施例に記載の不可避不純物とは、含有量０．０１質量％未満の不純物を示す。 Specifically, the composition of components contained in the Ag—Cu alloy plate and the joining plate of the

production methods

1 and 2 of the present invention is shown in Table 1, and the Ag—Cu alloy plate and the joining plate of the production methods 3 to 4 of the present invention are shown in Table 1. The component composition contained is listed in Table 3. In addition, Tables 1 and 3 also show the composition of components contained in the Ag—Cu alloy plate of the comparative example. Corresponding to Table 1 or Table 3, internal oxidation temperature, internal oxidation time, oxygen partial pressure, average particle size of oxide, workability of rolling after internal oxidation treatment and after clad processing, electrode material for thermal fuse Table 2 or Table 4 shows the final plate thickness and the final processing rate. As an evaluation method for each item described in Tables 1 to 4, the component composition contained in the Ag—Cu alloy plate and the joining plate is quantitatively analyzed using a wavelength dispersive electron microscope and an ICP emission analyzer. The remaining Ag and inevitable impurities are described as remaining. In addition, the inevitable impurities described in the examples of the present invention indicate impurities having a content of less than 0.01% by mass.

　接合性は、製造方法１～４で得られた完全焼鈍後の各クラッド板に対し、ＪＩＳ　Ｚ　２２４８に規定する押曲げ法に従い、１８０゜曲げ後、密着曲げ試験を行い、湾曲部の割れや剥離の有無により接合性を評価した。湾曲部に割れや剥離が認められるものを×、湾曲部に割れや剥離が認められずに接合性に優れているものを○と評価した。なお、接合性の評価が×であっても、下記の加工性の評価がＡ～Ｃ、かつその他の評価項目の評価が○であれば、温度ヒューズ用可動電極として好適に使用できる。 Bondability is determined by subjecting each clad plate obtained by manufacturing methods 1 to 4 to a fully-annealed clad plate after 180 ° bending according to the pressing method defined in JIS Z 2248, and performing a close-contact bending test. Bondability was evaluated by the presence or absence of peeling. The case where cracks and peeling were observed in the curved portion was evaluated as x, and the case where cracks and separation were not observed in the curved portion and excellent in bondability was evaluated as ◯. Even if the bondability evaluation is x, if the following processability evaluation is A to C and the evaluation of other evaluation items is ○, it can be suitably used as a movable electrode for a thermal fuse.

　曲げ加工性（接合性）は、各製造方法で最終板厚まで加工した各種電極材料の試験片の一端を固定した上で、９０°繰り返し曲げ試験を行い、試験片に亀裂が発生するまでの曲げ回数を計測し、その曲げ回数で接合性を評価した。この曲げ回数が１０回以上のものを評価Ａ、４回以上１０回未満のものを評価Ｂ、２回以上４回未満のものを評価Ｃとした。なお、所定形状の可動電極に加工する際、プレス加工によって曲げ加工を１回施すが、評価がＡ～Ｃであれば十分な信頼性を有する可動電極へ加工できる。なお、本発明のいずれの製造方法においても、得られた可動電極材料は各層の界面剥離は発生せず、基板層で破断し、極めて良好な接合性を有する可動電極材料を得ることができた。 Bending workability (bondability) is determined by fixing a test piece of various electrode materials processed to the final plate thickness by each manufacturing method and then performing a 90 ° repeated bending test until the test piece is cracked. The number of bends was measured, and the bondability was evaluated based on the number of bends. The number of bending was 10 times or more was evaluated as A, the number of 4 times or more and less than 10 times was evaluated as B, and the case of 2 times or more and less than 4 times was evaluated as C. In addition, when processing into a movable electrode having a predetermined shape, bending is performed once by pressing, but if the evaluation is A to C, the movable electrode can be processed with sufficient reliability. In any of the production methods of the present invention, the obtained movable electrode material did not cause interfacial delamination between layers, and was broken at the substrate layer to obtain a movable electrode material having extremely good bonding properties. .

　加工性は、熱処理による硬さ調整前の最終板厚における最終加工率が断面減少率で８０％以上に冷間圧延加工できたものを○、できなかったものを×と評価した。評価×とした理由としては、圧延加工時の割れおよび破断と内部酸化層の割れ等が挙げられる。なお、本発明のいずれの製造方法においても、比較例と比べて、良好な加工性が得られた。さらに、製造方法１～２では基板層に無酸素Ｃｕを用い、製造方法３～４では基板層にＣｕ合金を用いたが、加工性に差異は認められなかった。 The workability was evaluated as “◯” when the final processing rate in the final plate thickness before the hardness adjustment by heat treatment was cold-rolled to 80% or more in terms of the cross-sectional reduction rate, and “×” when it was not possible. Reasons for evaluation x include cracks and breaks during rolling, cracks in the internal oxide layer, and the like. In any of the production methods of the present invention, good workability was obtained as compared with the comparative example. Furthermore, in

manufacturing methods

1 and 2, oxygen-free Cu was used for the substrate layer, and in

manufacturing methods

3 and 4, a Cu alloy was used for the substrate layer, but no difference in workability was observed.

　酸化物の平均粒径は、温度ヒューズ用可動電極材料の断面を金属顕微鏡にて、１０００倍で酸化物粒子の平均粒径を計測した。平均粒径が０．５～５μｍの範囲のものを○、平均粒径が０．５～５μｍの範囲外のものを×と評価した。なお、本発明のいずれの内部酸化条件においても、良好な酸化物の平均粒径が得られた。 The average particle size of the oxide particles was measured at 1000 times the cross section of the movable electrode material for the thermal fuse with a metal microscope. A sample having an average particle size in the range of 0.5 to 5 μm was evaluated as ◯, and a sample having an average particle size outside the range of 0.5 to 5 μm was evaluated as ×. In addition, in any internal oxidation conditions of the present invention, a good average oxide particle size was obtained.

比較例
　比較例として、板厚０．５ｍｍのＡｇ－Ｃｕ合金板に対し、内部酸化炉中で５００℃～７５０℃、４８時間、酸素分圧０．１～２ＭＰａの条件で内部酸化処理を行い、表層両面に酸化物を含有する内部酸化層４および中層部に酸化物希薄層７を形成したＡｇ－酸化物合金板（図６）とし、完全焼鈍を施した後、最終板厚（０．１ｍｍ以下）における最終加工率が断面減少率で８０％以上になるように冷間圧延加工を施した電極材料種類Ｎｏ．４１～４７の詳細を表１～４に併記する。比較例の内部酸化時間を４８時間に統一した理由としては、比較例のＡｇ－Ｃｕ合金板の板厚において酸化物希薄層７が確実に形成され得る時間であるためである。 Comparative Example As a comparative example, an internal oxidation treatment was performed on an Ag—Cu alloy plate having a thickness of 0.5 mm in an internal oxidation furnace under conditions of 500 ° C. to 750 ° C. for 48 hours and an oxygen partial pressure of 0.1 to 2 MPa. An Ag-oxide alloy plate (FIG. 6) in which an inner oxide layer 4 containing an oxide on both surface layers and an oxide thin layer 7 in the middle layer portion were formed, and after final annealing, the final thickness (0. 1 mm or less), the electrode material type No. which has been cold-rolled so that the final processing rate in the cross-section reduction rate is 80% or more. Details of 41 to 47 are also shown in Tables 1 to 4. The reason why the internal oxidation time of the comparative example is unified to 48 hours is that the oxide thin layer 7 can be surely formed in the thickness of the Ag—Cu alloy plate of the comparative example.

　比較例における酸化物希薄層７の定義とは、内部酸化処理を施したＡｇ－Ｃｕ合金板の長手方向断面の中央部に位置し、酸化物の含有量が１質量％より低く、かつ断面比率で１０％以下の範囲の層のことをいう。 The definition of the diluted oxide layer 7 in the comparative example is located at the center of the longitudinal cross section of the Ag-Cu alloy plate subjected to the internal oxidation treatment, the oxide content is lower than 1% by mass, and the cross-sectional ratio Means a layer in the range of 10% or less.

　次に、本発明の製造方法を説明する。

製造方法１
　本製造方法による実施例を表１および表２に示す。電極材料種類Ｎｏ.１～４０に当該する所望の各組成のＡｇ－Ｃｕ合金および不可避不純物を含む無酸素Ｃｕを溶解法で作製した。Ａｇ－Ｃｕ合金は、圧延加工を施し、Ａｇ－Ｃｕ合金層１となるＡｇ－Ｃｕ合金板（板厚０．５ｍｍ）とした。無酸素Ｃｕは、押出加工および圧延加工を施し、基板層２となるＣｕ板（板厚２ｍｍ）とした。 Next, the manufacturing method of this invention is demonstrated.

Manufacturing method 1
Examples according to this production method are shown in Tables 1 and 2. An Ag—Cu alloy having each desired composition corresponding to the electrode material types No. 1 to 40 and oxygen-free Cu containing inevitable impurities were prepared by a melting method. The Ag—Cu alloy was rolled to obtain an Ag—Cu alloy plate (plate thickness 0.5 mm) to be the Ag—Cu alloy layer 1. Oxygen-free Cu was subjected to extrusion processing and rolling processing to form a Cu plate (plate thickness 2 mm) to be the substrate layer 2.

　その後、上記Ａｇ－Ｃｕ合金板および上記Ｃｕ板に表面処理を施し、これらをクラッド加工および冷間圧延加工することで、板厚が０．５ｍｍであり、基板層２の長手方向の表裏両面にＡｇ－Ｃｕ合金層１を有する多層構造の３層クラッド板（図１）を得た。 Thereafter, the Ag—Cu alloy plate and the Cu plate are subjected to surface treatment, and these are subjected to clad processing and cold rolling to have a plate thickness of 0.5 mm on both the front and back surfaces of the substrate layer 2 in the longitudinal direction. A three-layer clad plate (FIG. 1) having a multilayer structure having an Ag—Cu alloy layer 1 was obtained.

　クラッド加工の条件としては、Ａｇ－Ｃｕ合金板およびＣｕ板のそれぞれに２つの通電ロールを設け、還元雰囲気下でそれぞれの通電ロール間を電流加熱しつつ、Ｃｕ板の長手方向の表裏両面にＡｇ－Ｃｕ合金板が重なるように圧着ロール間へ連続的に送り込み、圧下率５０％の熱間圧延を施した。還元雰囲気は、窒素と水素の混合比率が５：２になるように調整した。電流加熱の条件は、材料が圧着ロール間を通過する際、Ｃｕ板およびＡｇ－Ｃｕ合金板の温度を４００℃になるように電流値を調整した。温度を４００℃に固定した理由は試験条件を揃える為であり、温度条件としては２００～７５０℃の範囲が好ましい。 As the conditions for the clad processing, two energizing rolls are provided on each of the Ag—Cu alloy plate and the Cu plate, and current is heated between the energizing rolls in a reducing atmosphere, while Ag is formed on both front and back surfaces of the Cu plate in the longitudinal direction. -Continuous feeding between the pressure-bonding rolls so that the Cu alloy plates overlap, and hot rolling with a reduction rate of 50% was performed. The reducing atmosphere was adjusted so that the mixing ratio of nitrogen and hydrogen was 5: 2. The current heating conditions were such that the current value was adjusted so that the temperature of the Cu plate and the Ag—Cu alloy plate was 400 ° C. when the material passed between the pressure-bonding rolls. The reason for fixing the temperature at 400 ° C. is to align the test conditions, and the temperature condition is preferably in the range of 200 to 750 ° C.

　上記３層クラッド板を、内部酸化炉中で５５０～７５０℃、０．２５～３６時間、酸素分圧０．１～２ＭＰａの条件で内部酸化処理を行った。この際、各層における組成および層厚により上記各範囲内で条件を選択し、上記３層クラッド板の表裏両面の表層に酸化物３を含有する内部酸化層４を形成し、中層部に未酸化層５、材料中心部に基板層２を持つ多層構造（図２）を有するようにした。 The above three-layer clad plate was internally oxidized in an internal oxidation furnace under the conditions of 550 to 750 ° C., 0.25 to 36 hours, and oxygen partial pressure of 0.1 to 2 MPa. At this time, conditions are selected within the above ranges depending on the composition and thickness of each layer, and an internal oxide layer 4 containing oxide 3 is formed on the front and back surfaces of the three-layer clad plate, and unoxidized in the middle layer portion. A multilayer structure (FIG. 2) having a layer 5 and a substrate layer 2 at the center of the material was provided.

　次に、試験条件を揃えるために上記内部酸化後の３層クラッド板を完全焼鈍後、図２に示される多層構造を有したまま冷間圧延加工を施して、最終板厚を０．１ｍｍ以下に加工し、温度ヒューズ用電極材料を作製した。 Next, in order to make the test conditions uniform, the above-mentioned three-layer clad plate after internal oxidation is completely annealed and then cold-rolled with the multilayer structure shown in FIG. The electrode material for thermal fuses was produced.

製造方法２
　本製造方法による実施例を表１および表２に示す。電極材料種類Ｎｏ.１～４０に当該する接合板となる所望の各組成の合金および不可避不純物を含む無酸素Ｃｕを溶解法で作製した。接合板となる所望の組成の合金は、圧延加工を施し、接合板（板厚０．５ｍｍ）とした。無酸素Ｃｕは、押出加工および圧延加工を施し、基板層２となるＣｕ板（板厚３．０ｍｍ）とした。さらに、製造方法１と同様の製造方法にて電極材料種類Ｎｏ.１～４０に当該する各組成、かつ同寸法のＡｇ－Ｃｕ合金板を得た。 Manufacturing method 2
Examples according to this production method are shown in Tables 1 and 2. An alloy of each desired composition and an oxygen-free Cu containing unavoidable impurities to be the bonding plates corresponding to the electrode material types No. 1 to 40 were prepared by a melting method. An alloy having a desired composition to be a bonded plate was subjected to a rolling process to obtain a bonded plate (plate thickness 0.5 mm). Oxygen-free Cu was subjected to extrusion processing and rolling processing to form a Cu plate (plate thickness 3.0 mm) to be the substrate layer 2. Further, Ag—Cu alloy plates having the same composition and the same dimensions as electrode material types No. 1 to 40 were obtained by the same production method as Production method 1.

　その後、上記接合板および上記Ｃｕ板に表面処理を施し、これらをクラッド加工および冷間圧延加工することで、板厚が２．０ｍｍであり、基板層２の長手方向の表裏両面に接合層６を有する多層構造の３層クラッド板（図３）を得た。クラッド加工の条件としては、Ａｇ－Ｃｕ合金板を接合板に置き換えた以外は製造方法１と同条件とした。 Thereafter, the bonding plate and the Cu plate are subjected to surface treatment, and these are subjected to cladding processing and cold rolling processing, whereby the plate thickness is 2.0 mm, and the bonding layer 6 is formed on both the front and back surfaces of the substrate layer 2 in the longitudinal direction. A three-layer clad plate having a multilayer structure (FIG. 3) was obtained. The conditions for the clad processing were the same as those in Manufacturing Method 1 except that the Ag—Cu alloy plate was replaced with a bonded plate.

　その後、製造方法１と同条件で作製したＡｇ－Ｃｕ合金板および上記３層クラッド板に表面処理を施し、これらをクラッド加工および冷間圧延加工することで、板厚が０．５ｍｍであり、基板層２の長手方向の表裏両面に接合層６およびＡｇ－Ｃｕ合金層１を有する多層構造の５層クラッド板（図４）を得た。クラッド加工の条件としては、Ｃｕ板を３層クラッド板に置き換えた以外は製造方法１と同条件とした。 Thereafter, the Ag—Cu alloy plate and the three-layer clad plate produced under the same conditions as in the production method 1 were subjected to surface treatment, and the plate thickness was 0.5 mm by clad processing and cold rolling. A multi-layered five-layer clad plate (FIG. 4) having a bonding layer 6 and an Ag—Cu alloy layer 1 on both front and back surfaces in the longitudinal direction of the substrate layer 2 was obtained. The conditions for the clad processing were the same as those in Production Method 1 except that the Cu plate was replaced with a three-layer clad plate.

　上記５層クラッド板を製造方法１と同条件で内部酸化処理を行った。この際、各層における組成および層厚により上記各範囲内で条件を選択し、上記５層クラッド板の表裏両面の表層に酸化物３を含有する内部酸化層４を形成し、中層部に未酸化層５および接合層６、材料中心部に基板層２を持つ多層構造（図５）を有するようにした。 The above five-layer clad plate was subjected to internal oxidation treatment under the same conditions as in Production Method 1. At this time, conditions within the above ranges are selected according to the composition and layer thickness of each layer, and an internal oxide layer 4 containing oxide 3 is formed on the front and back surfaces of the five-layer clad plate, and unoxidized in the middle layer portion. The layer 5 and the bonding layer 6 have a multilayer structure (FIG. 5) having the substrate layer 2 at the center of the material.

　次に、試験条件を揃えるために上記内部酸化後の５層クラッド板を完全焼鈍後、図５に示される多層構造を有したまま冷間圧延加工を施して、最終板厚を０．１ｍｍ以下に加工し、温度ヒューズ用電極材料を作製した。 Next, in order to make the test conditions uniform, the above-mentioned internally oxidized five-layer clad plate is completely annealed and then cold-rolled with the multilayer structure shown in FIG. The electrode material for thermal fuses was produced.

製造方法３
　本製造方法による実施例を表３および表４に示す。Ｓｎを０．２質量％含むＣｕ合金を溶解法で作製した。Ｃｕ合金は、押出加工および圧延加工を施し、基板層２となるＣｕ合金板（板厚２．０ｍｍ）とした。 Manufacturing method 3
Examples according to this production method are shown in Tables 3 and 4. A Cu alloy containing 0.2% by mass of Sn was prepared by a melting method. The Cu alloy was subjected to extrusion processing and rolling processing to obtain a Cu alloy plate (plate thickness 2.0 mm) to be the substrate layer 2.

　次に、Ｃｕ板を上記Ｃｕ合金板に置き換えた以外は製造方法1と同様にして、図２に示される多層構造を有し、かつ最終板厚が０．１ｍｍ以下である、温度ヒューズ用電極材料を作製した。 Next, a thermal fuse electrode having the multilayer structure shown in FIG. 2 and having a final thickness of 0.1 mm or less is the same as in manufacturing method 1 except that the Cu plate is replaced with the Cu alloy plate. The material was made.

製造方法４
　本製造方法による実施例を表３および表４に示す。Ｓｎを０．２質量％含むＣｕ合金を溶解法で作製した。Ｃｕ合金は、押出加工および圧延加工を施し、基板層２となるＣｕ合金板（板厚３．０ｍｍ）とした。 Manufacturing method 4
Examples according to this production method are shown in Tables 3 and 4. A Cu alloy containing 0.2% by mass of Sn was prepared by a melting method. The Cu alloy was subjected to extrusion processing and rolling processing to obtain a Cu alloy plate (plate thickness 3.0 mm) to be the substrate layer 2.

　次に、Ｃｕ板を上記Ｃｕ合金板に置き換えた以外は製造方法２と同様にして、図５に示される多層構造を有し、かつ最終板厚が０．１ｍｍ以下である、温度ヒューズ用電極材料を作製した。 Next, a thermal fuse electrode having the multilayer structure shown in FIG. 5 and having a final thickness of 0.1 mm or less is the same as in manufacturing method 2 except that the Cu plate is replaced with the Cu alloy plate. The material was made.

　実施例および比較例の温度ヒューズ用電極材料は、必要に応じて熱処理によって所望の硬さに調整した後、プレス加工等によって所定形状の可動電極に加工することで、感温材が作動温度で溶融して圧縮ばね除荷し、圧縮ばねが伸張することによって、圧縮ばねにより圧接されていた可動電極とリード線とが離隔して電流を遮断する市販の典型的な感温ペレット型温度ヒューズに好適に利用できる。 The thermal fuse electrode materials of the examples and comparative examples are adjusted to a desired hardness by heat treatment as necessary, and then processed into a movable electrode having a predetermined shape by pressing or the like, so that the temperature sensitive material is at the operating temperature. It melts and unloads the compression spring, and when the compression spring expands, the movable electrode pressed by the compression spring is separated from the lead wire to cut off the current, and it becomes a typical temperature-sensitive pellet type temperature fuse on the market It can be suitably used.

　そこで、実施例および比較例の温度ヒューズ用電極材料を必要に応じて熱処理によって所望の硬さに調整した後に、プレス加工によって所定形状の可動電極に加工し、上記可動電極を感温ペレット型温度ヒューズに実装し、ＤＣ３０Ｖ、２０Ａ、昇温速度１℃毎分に設定して通電試験および電流遮断試験を行った結果を表２および表４に示す。 Therefore, after adjusting the temperature fuse electrode material of the example and the comparative example to a desired hardness by heat treatment as necessary, it is processed into a movable electrode of a predetermined shape by pressing, and the movable electrode is subjected to a temperature sensitive pellet type temperature. Tables 2 and 4 show the results of conducting an energization test and a current interruption test with a fuse mounted, DC30V, 20A, and a heating rate of 1 ° C per minute.

　通電試験は、温度ヒューズに１０分間通電して、試験前後の温度ヒューズ金属ケースの表面での温度差が１０℃未満のものを○とし、１０℃以上のものを×と評価した。 In the energization test, the temperature fuse was energized for 10 minutes, and the temperature difference on the surface of the temperature fuse metal case before and after the test was less than 10 ° C., and the temperature difference of 10 ° C. or more was evaluated as x.

　電流遮断試験は、温度ヒューズに１０分間通電した後、通電を続けながら試験環境の温度を、動作温度よりも１０℃高い温度に昇温し、温度ヒューズを実際に動作させ、電流の遮断を試みた。試験後、可動電極とリード線とが溶着しなかったもの、つまり電流を遮断できたものを○と評価した。 In the current interruption test, after energizing the thermal fuse for 10 minutes, the temperature of the test environment was raised to 10 ° C higher than the operating temperature while continuing to energize, and the thermal fuse was actually operated to try to interrupt the current. It was. After the test, a case where the movable electrode and the lead wire were not welded, that is, a case where the current could be interrupted, was evaluated as ◯.

　１　Ａｇ－Ｃｕ合金層
　２　基板層
　３　酸化物
　４　内部酸化層
　５　未酸化層
　６　接合層
　７　酸化物希薄層 DESCRIPTION OF SYMBOLS 1 Ag-Cu alloy layer 2 Substrate layer 3 Oxide 4 Internal oxide layer 5 Non-oxidized layer 6 Bonding layer 7 Diluted oxide layer

Claims

　感温材が作動温度で溶融して圧縮ばねの発力を除荷し、圧縮ばねが伸張することによって、圧縮ばねにより圧接されていた可動電極とリード線とが離隔して電流を遮断する温度ヒューズの電極材料において、
　可動電極の材料として、基板の表裏両面にＡｇ－Ｃｕ合金からなるＡｇ－Ｃｕ合金板を１層以上設けることによって、基板層とＡｇ－Ｃｕ合金層とを形成し、これに内部酸化処理を施すことで前記Ａｇ－Ｃｕ合金層に内部酸化層を形成した多層構造であることを特徴とする温度ヒューズ用電極材料。 Temperature at which the temperature sensitive material melts at the operating temperature, unloads the force generated by the compression spring, and the compression spring expands, causing the movable electrode and the lead wire, which are pressed by the compression spring, to separate and cut off the current. In the fuse electrode material,
As a material of the movable electrode, by providing one or more Ag—Cu alloy plates made of Ag—Cu alloy on both the front and back surfaces of the substrate, a substrate layer and an Ag—Cu alloy layer are formed and subjected to internal oxidation treatment. A thermal fuse electrode material having a multilayer structure in which an internal oxide layer is formed on the Ag—Cu alloy layer.
　感温材が作動温度で溶融して圧縮ばねの発力を除荷し、圧縮ばねが伸張することによって、圧縮ばねにより圧接されていた可動電極とリード線とが離隔して電流を遮断する温度ヒューズの電極材料において、
　可動電極の材料として、基板の表裏両面にＡｇ－Ｃｕ合金からなるＡｇ－Ｃｕ合金板および接合板を１層以上設けることによって、基板層に隣接する接合層の表裏両面にＡｇ－Ｃｕ合金層を形成し、かつ前記接合層を前記基板層と前記Ａｇ－Ｃｕ合金層との界面に形成し、これに内部酸化処理を施すことで前記Ａｇ－Ｃｕ合金層、もしくは前記Ａｇ－Ｃｕ合金層および前記接合層に内部酸化層を形成した多層構造であることを特徴とする温度ヒューズ用電極材料。 Temperature at which the temperature sensitive material melts at the operating temperature, unloads the force generated by the compression spring, and the compression spring expands, causing the movable electrode and the lead wire, which are pressed by the compression spring, to separate and cut off the current. In the fuse electrode material,
As a material for the movable electrode, by providing one or more Ag—Cu alloy plates and joining plates made of an Ag—Cu alloy on both front and back surfaces of the substrate, Ag—Cu alloy layers are formed on both front and back surfaces of the joining layer adjacent to the substrate layer. And forming the bonding layer at the interface between the substrate layer and the Ag—Cu alloy layer, and subjecting this to an internal oxidation treatment, thereby allowing the Ag—Cu alloy layer or the Ag—Cu alloy layer and the A temperature fuse electrode material having a multilayer structure in which an internal oxide layer is formed in a bonding layer.
　請求項１または請求項２において、基材および基板層の材質がＣｕまたはＣｕ合金であることを特徴とする温度ヒューズ用電極材料。 3. The thermal fuse electrode material according to claim 1, wherein the material of the base material and the substrate layer is Cu or a Cu alloy.
　請求項１または請求項２において、内部酸化処理前のＡｇ－Ｃｕ合金層の組成がＣｕを１～５０質量％含み、かつ残部がＡｇおよび不可避不純物を含む合金であることを特徴とする温度ヒューズ用電極材料。 3. The thermal fuse according to claim 1, wherein the composition of the Ag—Cu alloy layer before the internal oxidation treatment is an alloy containing 1 to 50% by mass of Cu and the balance containing Ag and inevitable impurities. Electrode material.
　請求項１または請求項２において、内部酸化処理前のＡｇ－Ｃｕ合金層の組成がＣｕを１～５０質量％含み、さらにＳｎ、Ｉｎ、Ｔｉ、Ｆｅ、ＮｉおよびＣｏの群から選ばれた少なくとも１種を０．０１～５質量％含み、かつ残部がＡｇおよび不可避不純物を含む合金であることを特徴とする温度ヒューズ用電極材料。 3. The composition of claim 1, wherein the composition of the Ag—Cu alloy layer before the internal oxidation treatment includes 1 to 50 mass% of Cu, and is further selected from the group consisting of Sn, In, Ti, Fe, Ni and Co. An electrode material for a thermal fuse, characterized in that one kind is contained in an amount of 0.01 to 5% by mass and the balance is an alloy containing Ag and inevitable impurities.
　請求項２において、内部酸化処理前の接合層の組成が、Ｃｕを０．０１～２８質量％含み、かつ残部がＡｇおよび不可避不純物を含む合金、もしくは不可避不純物を含む純Ａｇであることを特徴とする温度ヒューズ用電極材料。 The composition of the bonding layer according to claim 2, wherein the composition of the bonding layer before the internal oxidation treatment is 0.01 to 28% by mass of Cu and the balance is an alloy containing Ag and inevitable impurities, or pure Ag containing inevitable impurities. Thermal fuse electrode material.
　請求項１または請求項２において、内部酸化処理を施したＡｇ－Ｃｕ合金層の表層、もしくは内部酸化処理を施した接合層の一部およびＡｇ－Ｃｕ合金層において、内部酸化層を有し、かつ隣接する基板層側の残部は未酸化層を有していることを特徴とする温度ヒューズ用電極材料。 In Claim 1 or Claim 2, the surface layer of the Ag-Cu alloy layer subjected to the internal oxidation treatment, or a part of the bonding layer subjected to the internal oxidation treatment and the Ag-Cu alloy layer have an internal oxidation layer, An electrode material for a thermal fuse, wherein the remaining part on the side of the adjacent substrate layer has an unoxidized layer.
　請求項１に記載の温度ヒューズ用電極材料の製造方法において、基板の表裏両面にＡｇ－Ｃｕ合金板をクラッド加工することによって３層クラッド板を形成する工程と、前記３層クラッド板の表裏両面に内部酸化処理を行う工程と、この内部酸化処理後の材料に塑性加工および／もしくは熱処理を施す工程とを備え、薄板化後も材料中心部に基板層を有し、かつＡｇ－Ｃｕ合金層に内部酸化層が形成された多層構造を有することを特徴とする温度ヒューズ用電極材料の製造方法。 2. The method for producing an electrode material for a thermal fuse according to claim 1, wherein a step of forming a three-layer clad plate by clad an Ag—Cu alloy plate on both front and back surfaces of the substrate; And a step of subjecting the material after the internal oxidation treatment to plastic working and / or heat treatment, having a substrate layer at the center of the material even after being thinned, and an Ag—Cu alloy layer A method for producing an electrode material for a thermal fuse, which has a multilayer structure in which an internal oxide layer is formed.
　請求項２に記載の温度ヒューズ用電極材料の製造方法において、基板の表裏両面に接合板をクラッド加工し、さらに前記材料Ａｇ－Ｃｕ合金板をクラッド加工することによって５層クラッド板を形成する工程と、前記５層クラッド板の表裏両面に内部酸化処理を行う工程と、この内部酸化処理後の材料に塑性加工および／もしくは熱処理を施す工程とを備え、薄板化後も材料中心部に基板層、この基板層に隣接する接合層を有し、かつＡｇ－Ｃｕ合金層もしくはＡｇ－Ｃｕ合金層および接合層に内部酸化層が形成された多層構造を有することを特徴とする温度ヒューズ用電極材料の製造方法。 3. The method of manufacturing a thermal fuse electrode material according to claim 2, wherein a clad plate is clad on both the front and back surfaces of the substrate, and further, the material Ag—Cu alloy plate is clad to form a five-layer clad plate. And a step of performing internal oxidation treatment on both the front and back surfaces of the five-layer clad plate, and a step of subjecting the material after the internal oxidation treatment to plastic working and / or heat treatment, and the substrate layer in the center of the material even after thinning An electrode material for a thermal fuse having a bonding layer adjacent to the substrate layer and a multilayer structure in which an Ag—Cu alloy layer or an Ag—Cu alloy layer and an internal oxide layer are formed in the bonding layer Manufacturing method.
　請求項８または請求項９において、内部酸化処理の条件が、内部酸化炉中で５００℃～７５０℃、０．２５時間以上、酸素分圧０．１～２ＭＰａの条件で行うことを特徴とする温度ヒューズ用電極材料の製造方法。 9. The internal oxidation treatment according to claim 8 or 9, characterized in that the internal oxidation treatment is performed in an internal oxidation furnace under conditions of 500 ° C. to 750 ° C., 0.25 hours or more, and an oxygen partial pressure of 0.1 to 2 MPa. Manufacturing method of electrode material for thermal fuse.