JPWO2014091631A1 - Electrode material for thermal fuse and method for manufacturing the same - Google Patents
Electrode material for thermal fuse and method for manufacturing the same Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title abstract description 36
- 239000010410 layer Substances 0.000 claims abstract description 288
- 229910052751 metal Inorganic materials 0.000 claims abstract description 137
- 239000002184 metal Substances 0.000 claims abstract description 137
- 239000000463 material Substances 0.000 claims abstract description 94
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 71
- 230000003647 oxidation Effects 0.000 claims abstract description 70
- 239000000758 substrate Substances 0.000 claims abstract description 69
- 238000009792 diffusion process Methods 0.000 claims abstract description 44
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 25
- 239000002344 surface layer Substances 0.000 claims abstract description 24
- 238000005275 alloying Methods 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 31
- 239000000956 alloy Substances 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 229910052718 tin Inorganic materials 0.000 claims description 17
- 229910052738 indium Inorganic materials 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 13
- 230000006835 compression Effects 0.000 claims description 12
- 238000007906 compression Methods 0.000 claims description 12
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 10
- 230000036961 partial effect Effects 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 4
- 238000010030 laminating Methods 0.000 abstract description 10
- 238000007747 plating Methods 0.000 description 33
- 239000011241 protective layer Substances 0.000 description 29
- 238000005096 rolling process Methods 0.000 description 23
- 239000002245 particle Substances 0.000 description 22
- 239000002356 single layer Substances 0.000 description 20
- 238000005498 polishing Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 13
- 238000004140 cleaning Methods 0.000 description 12
- 238000012545 processing Methods 0.000 description 11
- 238000003466 welding Methods 0.000 description 11
- 229910017944 Ag—Cu Inorganic materials 0.000 description 10
- 238000005238 degreasing Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000004381 surface treatment Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 230000000875 corresponding effect Effects 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 6
- 238000003475 lamination Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 4
- 239000008188 pellet Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910017755 Cu-Sn Inorganic materials 0.000 description 1
- 229910017927 Cu—Sn Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000010288 cold spraying Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H37/00—Thermally-actuated switches
- H01H37/74—Switches in which only the opening movement or only the closing movement of a contact is effected by heating or cooling
- H01H37/76—Contact member actuated by melting of fusible material, actuated due to burning of combustible material or due to explosion of explosive material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
- C22C5/08—Alloys based on silver with copper as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H85/00—Protective devices in which the current flows through a part of fusible material and this current is interrupted by displacement of the fusible material when this current becomes excessive
- H01H85/02—Details
- H01H85/04—Fuses, i.e. expendable parts of the protective device, e.g. cartridges
- H01H85/05—Component parts thereof
- H01H85/055—Fusible members
- H01H85/06—Fusible members characterised by the fusible material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H37/00—Thermally-actuated switches
- H01H37/74—Switches in which only the opening movement or only the closing movement of a contact is effected by heating or cooling
- H01H37/76—Contact member actuated by melting of fusible material, actuated due to burning of combustible material or due to explosion of explosive material
- H01H2037/768—Contact member actuated by melting of fusible material, actuated due to burning of combustible material or due to explosion of explosive material characterised by the composition of the fusible material
Abstract
本発明は、基板に対して性質の異なる１種類以上の金属層を積層して形成される、多層構造材を用いた温度ヒューズ用電極材料およびその製造方法に関する。ＣｕもしくはＣｕ合金からなる基板の表裏両面に、１種以上の金属層を少なくとも１層が積層された前記基板および前記金属層からなる多層構造材とし、少なくとも１層の金属層を隣接する他の層へ拡散および合金化させて拡散合金化層を形成し、さらにこの多層構造材に内部酸化処理を施して多層構造材の表裏両面の少なくとも片面の表層に内部酸化層が形成された多層構造を有する温度ヒューズ用電極材料とした。The present invention relates to a thermal fuse electrode material using a multilayer structure material formed by laminating one or more kinds of metal layers having different properties on a substrate, and a method for manufacturing the same. A multilayer structure material composed of the substrate and the metal layer in which at least one metal layer is laminated on both front and back surfaces of a substrate made of Cu or Cu alloy, and at least one metal layer is adjacent to another A diffusion alloyed layer is formed by diffusing and alloying into a layer, and a multilayer structure in which an inner oxide layer is formed on at least one surface layer of the front and back surfaces of the multilayer structure material by subjecting the multilayer structure material to internal oxidation treatment. It was set as the electrode material for thermal fuses which has.
Description
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 attached to an electronic device or an electric appliance for home appliances in order to prevent those devices from becoming abnormally high temperature, 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。 This demand for welding resistance and material cost reduction can be addressed 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, with an increase in oxide, the Ag-oxide alloy has a marked reduction in rolling workability, making it difficult to process into a thin plate in the rolling step after internal oxidation.
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 was 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。 Moreover, since the internal oxide layer is hard to contain oxides, the rolling processability is poor, and it is 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。 An object of the present invention is to solve such a problem.
そこで本発明は、不可避不純物を含む純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対して、めっき法により、１種以上のＡｇ合金、１種以上のＣｕ合金、並びに、Ａｇ、Ｃｕ、Ｓｎ、Ｉｎ、Ｔｉ、Ｆｅ、Ｎｉ、Ｃｏの中から少なくとも１種以上選ばれた合金による金属層を、少なくとも１層以上積層させることによって構成される多層構造材を形成し、これに内部酸化処理を施すことで、前記多層構造材の中央部に基板層を有し、かつ前記多層構造材の表裏両面の表層のみもしくは片面の表層のみ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。熱処理時もしくは内部酸化処理時の熱により、前記金属層の少なくとも１層の構成成分の一部を、隣接する他の層へ拡散および合金化させて拡散合金化層を形成しても良い。なお、本発明でいう表層の定義とは、上記多層構造材の最表面から単層もしくは多層の金属層の層厚の総和以下の範囲のことを指すが、金属層の層厚の総和が基板層の表裏両面で相違する場合には、相違する総和の各々の範囲以下とする。 Therefore, the present invention provides one or more types of Ag alloy, one or more types of Cu alloy, and Ag, Cu by plating on both the front and back surfaces of the substrate made of pure Cu or Cu alloy containing inevitable impurities. , Sn, In, Ti, Fe, Ni, Co. A multilayered structure material is formed by laminating at least one metal layer made of an alloy selected from at least one kind from among, and internally oxidized For a thermal fuse having a multilayer structure in which a substrate layer is provided at the center of the multilayer structure material and an internal oxide layer is formed only on the front and back surfaces of the multilayer structure material or only on the surface layer of one surface. The electrode material is used. A diffusion alloyed layer may be formed by diffusing and alloying a part of constituent components of at least one of the metal layers into another adjacent layer by heat during heat treatment or internal oxidation treatment. The definition of the surface layer as used in the present invention refers to the range from the outermost surface of the multilayer structure material to the sum of the layer thicknesses of the single-layer or multilayer metal layers, but the sum of the metal layer thicknesses is the substrate. In the case where there is a difference between the front and back surfaces of the layer, the difference is not more than each range.
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を含まないため、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。もしくは、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の群から選ばれた少なくとも１種を含むＣｕ合金を用いても良い。 The composition of each layer is preferably pure Cu containing inevitable impurities in the substrate layer. Alternatively, at least one selected from the group consisting of Ti, Cr, Be, Si, Fe, Co, Zr, Zn, Sn, Ni, P, and Pb is used for the purpose of improving heat resistance, conductivity, or mechanical properties. A Cu alloy may be used.
上記金属層のＡｇ合金は、Ｃｕを０．０１〜５０質量％含み、かつ残部がＡｇおよび不可避不純物を含む合金が好ましい。 The Ag alloy of the metal layer is preferably an alloy containing 0.01 to 50% by mass of Cu and the balance containing Ag and inevitable impurities.
上記金属層のＣｕ合金は、Ａｇを０．０１〜５０質量％含み、かつ残部がＣｕおよび不可避不純物を含む合金が好ましい。 The Cu alloy of the metal layer is preferably an alloy containing 0.01 to 50% by mass of Ag and the balance containing Cu and inevitable impurities.
熱処理もしくは内部酸化処理により、少なくとも１層の金属層の構成成分の一部を隣接する他の金属層へ拡散および合金化させた後の拡散合金化層は、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または上記範囲の濃度勾配を有すること、あるいは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もしくは上記範囲の濃度勾配を有することが好ましい。 The diffusion alloying layer after diffusion and alloying a part of the constituent components of at least one metal layer to the other adjacent metal layer by heat treatment or internal oxidation treatment contains 1 to 50% by mass of Cu, And the balance is an alloy containing Ag and inevitable impurities, or has a concentration gradient in the above range, or contains 1 to 50% by mass of Cu, and at least one selected from the group consisting of Sn, In, Ti, Fe, Ni and Co It is preferable that the alloy contains 0.01 to 5% by mass of the seed, and the balance has an alloy containing Ag and inevitable impurities or a concentration gradient in the above range.
ここで、拡散合金化層のＣｕの含有量を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。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拡散合金化層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。また、酸化物含有量の増加に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ためである。 Here, the reason why the content of Cu in the diffusion alloyed layer is 1 to 50% by mass is that the oxide is insufficient when the Cu content is less than 1% by mass after the internal oxidation treatment, and the temperature fuse electrode This is because sufficient welding resistance for use as a material cannot be obtained. 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 diffusion alloyed layer by internal oxidation treatment, oxygen is mainly bonded 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. Moreover, it is because the workability of an internal oxide layer falls remarkably with the increase in oxide content, and it becomes easy to produce a crack in an internal oxide layer.
これらの理由により、内部酸化処理もしくは熱処理により構成成分の一部を隣接する他の層へ拡散および合金化させて拡散合金化層を形成する場合には、拡散後もしくは合金化後の金属層のＣｕの含有率が１〜５０質量％の範囲に収まるように積層する各金属層の層厚、内部酸化処理の条件および熱処理の条件を調整することが好ましい。 For these reasons, when a diffusion alloyed layer is formed by diffusing and alloying a part of the constituent components to other adjacent layers by internal oxidation treatment or heat treatment, the metal layer after diffusion or alloying is formed. It is preferable to adjust the layer thickness of each metal layer to be laminated, the conditions for internal oxidation treatment, and the conditions for heat treatment so that the Cu content is in the range of 1 to 50% by mass.
ただし、Ｃｕの含有量が１〜５０質量％の範囲であれば、拡散合金化層を形成せずに、Ａｇ合金またはＣｕ合金の金属層を単層で用いてもよい。 However, if the Cu content is in the range of 1 to 50% by mass, the metal layer of Ag alloy or Cu alloy may be used as a single layer without forming the diffusion alloyed layer.
さらに、多層構造材の最表面にＣｕが１質量％未満のＡｇ合金もしくはＡｇを積層させる場合には、上記と同じ理由により、これを隣接する他の金属層と内部酸化処理もしくは熱処理により拡散および合金化させて拡散合金化層を形成し、拡散合金化層のＣｕの含有率が１〜５０質量％に調整することが好ましい。 Further, when an Ag alloy or Ag having a Cu content of less than 1% by mass is laminated on the outermost surface of the multilayer structure material, for the same reason as described above, this is diffused by other internal metal layers and internal oxidation treatment or heat treatment. It is preferable to form a diffusion alloyed layer by alloying and adjust the Cu content of the diffusion alloyed layer to 1 to 50% by mass.
本発明における金属層の積層方法としては、電解めっき法が好ましい。電解めっき法は、金属層を構成する金属塩を含むめっき液を用いて、基板に電解でめっきを行う方法である。なお、無電解めっき法でも積層可能である。また、他の積層方法としては、クラッド法、スパッタリング法、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挙げられる。 As a method for laminating the metal layer in the present invention, an electrolytic plating method is preferable. The electrolytic plating method is a method in which a substrate is electrolytically plated using a plating solution containing a metal salt constituting a metal layer. It is also possible to stack by electroless plating. Other laminating methods include cladding by sputtering, sputtering, plasma spraying, gas spraying, high-speed flame spraying, cold spraying, etc., intermittent discharge in the air or liquid, discharge of pulses, etc. And lamination by vapor deposition methods such as PVD (Physical Vapor Deposition) and CVD (Chemical Vapor Deposition).
上記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、片面はクラッド法、反対側の面はめっき法としてもよい。 The method for manufacturing the thermal fuse electrode material according to the present invention may be a method combining the above manufacturing methods. For example, the substrate layer may be a material central portion, one side may be a cladding method, and the opposite surface may be a plating method. .
さらに、基板層を材料中央部として、各種層を表裏非対称に配置してもよい。例えば、片面の表層は内部酸化層、反対側の面の表層は後述する保護層としてもよい。 Furthermore, various layers may be arranged asymmetrically with the substrate layer as the material center. 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 protective layer described later.
本発明における電解めっき法では、表面処理を施した基板を、めっき浴に浸漬して金属層を形成する。本発明の金属層を形成する際の条件は、特に限定されないが、例えば、以下に示す条件とすることが好ましい。 In the electrolytic plating method in the present invention, the surface-treated substrate is immersed in a plating bath to form a metal layer. Although the conditions at the time of forming the metal layer of this invention are not specifically limited, For example, it is preferable to set it as the conditions shown below.
めっき浴に浸漬する時間は、目的とする金属層厚により適宜に決定する。金属層の厚みは特に限定されないが、０．５μｍ〜２００μｍの範囲であることが好ましい。金属層の厚みが上記範囲未満であると、金属層に対して内部酸化処理を施した後の内部酸化層厚が薄くなり、温度ヒューズ用可動電極として機能させる場合に、耐溶着性が不足して溶着が発生しやすくなる。また、金属層厚みが上記範囲を超えても、金属層を設けることによる効果に差はないが、めっき時間が長時間になり生産性が低下して製造費用が高くなるため好ましくない。 The time for immersion in the plating bath is appropriately determined depending on the target metal layer thickness. Although the thickness of a metal layer is not specifically limited, It is preferable that it is the range of 0.5 micrometer-200 micrometers. When the thickness of the metal layer is less than the above range, the thickness of the internal oxide layer after the internal oxidation treatment is performed on the metal layer becomes thin, and the welding resistance is insufficient when functioning as a movable electrode for a thermal fuse. As a result, welding is likely to occur. Even if the thickness of the metal layer exceeds the above range, there is no difference in the effect of providing the metal layer, but it is not preferable because the plating time becomes long and the productivity is lowered and the manufacturing cost is increased.
積層する金属層の層数は、基板の片面の多層金属層において最大９層までが好ましい。金属層の層数が上記範囲を超えても、金属層の層数を増やすことによる効果に差はないが、めっき時間が長時間になり、生産性が低下して製造費用が高くなるため、好ましくない。 The number of metal layers to be laminated is preferably up to 9 layers in the multilayer metal layer on one side of the substrate. Even if the number of layers of the metal layer exceeds the above range, there is no difference in the effect by increasing the number of layers of the metal layer, but because the plating time becomes long, productivity decreases and the manufacturing cost increases, It is not preferable.
少なくとも１層の金属層の構成成分の一部を、隣接する金属層へ拡散および合金化させる場合の拡散合金化層の層厚は、前記と同様の理由により、０．５〜１００μｍの範囲が好ましい。また、後述する保護層としての金属層の層厚においては、０．５μｍ〜２００μｍの範囲が好ましい。０．５μｍよりも薄い場合は、酸化処理時の基板への酸素の侵入を十分に妨げられないことがある。 The layer thickness of the diffusion alloyed layer when a part of the constituent components of at least one metal layer is diffused and alloyed to the adjacent metal layer is in the range of 0.5 to 100 μm for the same reason as described above. preferable. Moreover, in the layer thickness of the metal layer as a protective layer mentioned later, the range of 0.5 micrometer-200 micrometers is preferable. If the thickness is less than 0.5 μm, oxygen may not be sufficiently prevented from entering the substrate during the oxidation treatment.
めっき浴の温度は、めっき速度や形成される金属層の品質などを考慮して適宜決定できるが、２０℃〜８０℃の範囲とすることが好ましい。めっき浴の温度が２０℃未満であると、めっき速度が遅くなり、生産性に支障を来たす場合がある。また、めっき浴の温度が２０℃未満であると、金属層が硬くなり高電流密度で使えなくなる場合がある。めっき浴の温度が８０℃を超えると、金属層が粗面化し、光沢と均一電着性が悪くなる場合がある。 The temperature of the plating bath can be appropriately determined in consideration of the plating speed, the quality of the metal layer to be formed, etc., but is preferably in the range of 20 ° C to 80 ° C. If the temperature of the plating bath is less than 20 ° C., the plating rate becomes slow, which may hinder productivity. On the other hand, if the temperature of the plating bath is less than 20 ° C., the metal layer may become hard and cannot be used at a high current density. If the temperature of the plating bath exceeds 80 ° C., the metal layer may be roughened, and the gloss and throwing power may deteriorate.
めっき浴の電流密度は、めっき速度や形成される金属層の品質などを考慮して適宜決定できるが、０．１〜５０Ａ/ｄｍ2の範囲とすることが好ましい。めっき浴の電流密度が０．１Ａ/ｄｍ2未満であると、めっき速度が遅くなり、生産性に支障を来たす場合がある。また、めっき浴の電流密度が５０Ａ/ｄｍ2を超えると、めっき被膜が粗面化し、好ましくない。The current density of the plating bath is a like quality of the metal layer to be plated speed and form can be determined appropriately in consideration, it is preferably in the range of 0.1~50A / dm 2. When the current density of the plating bath is less than 0.1 A / dm 2 , the plating rate is slow, which may hinder productivity. On the other hand, when the current density of the plating bath exceeds 50 A / dm 2 , the plating film becomes rough, which is not preferable.
めっき浴のｐＨは、イオン供給源のめっき液浴組成の種類によって、適宜調整される。さらに、金属層の形成された多層構造材に対して、水や有機溶剤で洗浄する洗浄処理を必要に応じて行うことが好ましい。 The pH of the plating bath is appropriately adjusted depending on the type of the plating solution bath composition of the ion supply source. Furthermore, it is preferable to perform a cleaning process for cleaning the multilayer structure material on which the metal layer is formed with water or an organic solvent as necessary.
上記積層方法にて作製した多層構造材は、必要に応じて圧延加工および熱処理を施しても良い。なお、熱処理を施すことにより、隣接する金属層と拡散および合金化して拡散合金化層を形成させる効果のほかに、積層させた金属層を基板に定着させる効果がある。 The multilayer structure material produced by the above laminating method may be subjected to rolling and heat treatment as necessary. In addition to the effect of diffusion and alloying with an adjacent metal layer to form a diffusion alloyed layer, heat treatment has an effect of fixing the laminated metal layer to the substrate.
本発明は、上記積層方法にて作製した多層構造材の表層に内部酸化法を用いて内部酸化組織を形成することを特徴とするものである。 The present invention is characterized in that an internal oxidized structure is formed on a surface layer of a multilayer structure material produced by the above-described lamination method using an internal oxidation method.
上記金属層の積層の順として、1種以上のＡｇ合金、1種以上のＣｕ合金、ＡｇおよびＣｕの群から選ばれた少なくとも２種以上の金属層を上記基板に多層にして積層させる場合には、積層させる金属層と隣接する他の金属層とが異種金属になるように積層させることが好ましい。 When laminating at least two or more kinds of metal layers selected from the group of one or more kinds of Ag alloys, one or more kinds of Cu alloys, and Ag and Cu as the order of lamination of the metal layers in a multilayer on the substrate. Is preferably laminated so that the metal layer to be laminated and another adjacent metal layer are different metals.
なお、多層構造材の最表面には、ＣｕもしくはＣｕ合金は積層しないほうが好ましい。これは、内部酸化処理を施す多層構造材の表面付近において、Ｃｕの含有量が５０質量％を超えると、内部酸化処理により酸素を金属層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ためである。 In addition, it is preferable not to laminate | stack Cu or Cu alloy on the outermost surface of a multilayered structural material. In the vicinity of the surface of the multilayer structure material subjected to the internal oxidation treatment, when the Cu content exceeds 50% by mass, oxygen is mainly contained in the Cu layer even if oxygen is caused to penetrate into the metal layer by the internal oxidation treatment. This is because they bind to form an oxide film near the surface, and it is difficult to disperse the oxide particles in the Ag matrix.
Ｓｎ、Ｉｎ、Ｔｉ、Ｆｅ、およびＮｉの群から選ばれた少なくとも１種の金属層についても、多層構造材の最表面に当該金属層を積層すると、内部酸化処理により酸素を金属層中に侵入させようとしても、多層構造材の最表面付近で酸化皮膜を形成してしまい、内部酸化層が形成されない。多層構造材の表面付近で酸化皮膜が形成されると、接触抵抗が上昇することにより温度上昇を招くので、温度ヒューズ用電極材料として好ましくない。また、Ｓｎ、Ｉｎ、Ｔｉ、ＦｅおよびＮｉの群から選ばれた少なくとも１種の金属層においては、保護層を形成すること目的として積層することを除いて、単層で金属層中に積層されたまま内部酸化処理を施しても、前記単層より材料内部の内部酸化組織の形成が妨げられるので、内部酸化処理前に熱処理により隣接する他の金属層と拡散および合金化をする必要がある。この為、Ｓｎ、Ｉｎ、Ｔｉ、Ｆｅ、およびＮｉの群から選ばれた少なくとも１種の金属層においては、隣接する金属層がＡｇ、Ｃｕ、Ａｇ合金、もしくはＣｕ合金になるように積層させ、かつ隣接する金属層と拡散および合金化させることが好ましい。 For at least one metal layer selected from the group consisting of Sn, In, Ti, Fe, and Ni, when the metal layer is laminated on the outermost surface of the multilayer structure material, oxygen penetrates into the metal layer by internal oxidation treatment. Even if it tries to make it, an oxide film will be formed in the outermost surface vicinity of a multilayered structural material, and an internal oxide layer will not be formed. If an oxide film is formed in the vicinity of the surface of the multilayer structure material, the contact resistance increases and the temperature rises, which is not preferable as a temperature fuse electrode material. In addition, at least one metal layer selected from the group consisting of Sn, In, Ti, Fe and Ni is laminated in the metal layer as a single layer except that it is laminated for the purpose of forming a protective layer. Even if the internal oxidation treatment is performed as it is, the formation of the internal oxidation structure inside the material is prevented from the single layer, so it is necessary to diffuse and alloy with other metal layers adjacent to each other by heat treatment before the internal oxidation treatment. . Therefore, in at least one metal layer selected from the group consisting of Sn, In, Ti, Fe, and Ni, the adjacent metal layers are laminated so as to be Ag, Cu, Ag alloy, or Cu alloy, And it is preferable to diffuse and alloy with an adjacent metal layer.
Ｓｎ、Ｉｎ、Ｔｉ、Ｆｅ、およびＮｉの群から選ばれた少なくとも１種の金属層を、上記基板の表裏両面もしくは片面に、保護層を形成することを目的として積層させた場合には、内部酸化処理時の基板への酸素の侵入を妨げ、内部酸化層の剥離を防止する効果がある。この為、多層構造材の片面の表層のみに内部酸化組織を形成する場合においても、保護層として特に有効である。 When at least one metal layer selected from the group consisting of Sn, In, Ti, Fe and Ni is laminated for the purpose of forming a protective layer on both the front and back surfaces or one surface of the substrate, This has the effect of preventing oxygen from entering the substrate during the oxidation treatment and preventing the internal oxide layer from peeling off. For this reason, even when the internal oxide structure is formed only on the surface layer on one side of the multilayer structure material, it is particularly effective as a protective layer.
内部酸化法は、隣接する他の層と拡散および合金化が生じた拡散合金化層中、または単層金属層中において、Ａｇマトリックス中に含有されたＣｕが、多層構造材の表層からＡｇマトリックス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、材料内部から表層に向かって拡散する現象が生じる。 In the internal oxidation method, Cu contained in the Ag matrix is diffused from the surface layer of the multilayer structure material into the Ag matrix in the diffusion alloyed layer in which diffusion and alloying have occurred with other adjacent layers or in the single layer metal layer. By being combined with oxygen occluded therein, a process of depositing as an oxide in the Ag matrix is taken. At this time, the solute element Cu is diffused from the inside of the material toward the surface layer.
この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、上記多層構造材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、時間の経過により酸化物の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。このため、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 in which this solute element diffuses from the inside of the material toward the surface layer is due to the internal oxide layer formed by the oxide deposited from the material surface of the multilayer structure material to the inside, and the precipitation of the oxide over time. This is a phenomenon in which a difference in Cu concentration occurs between an unoxidized layer that has not occurred and Cu diffuses from the unoxidized layer toward the surface layer in order to fill the concentration gradient. For this reason, it always supplies oxygen exceeding the amount of oxygen necessary for the oxidation of other elements in the Ag matrix.
従来例として比較例に挙げたＡｇ−酸化物合金において、酸化物希薄層とは、所望組成のＡｇ−Ｃｕ合金に内部酸化処理を長時間施して内部酸化層を形成することで、時間の経過により酸化物の析出が起きていない未酸化層が無くなり、Ａｇ−Ｃｕ合金としてＡｇ中にあらかじめ含有された溶質元素であるＣｕがほぼ失われ、材料中心部に酸化物が希薄に形成された層のことをいう。なお、比較例における酸化物希薄層の定義とは、酸化物の濃度が約１質量％より低い層のことであり、Ａｇ−酸化物合金板の断面比率で１０％以下の範囲のことをいう。また、本発明における未酸化層の定義とは、内部酸化層とは別に、酸化物が含まれない層のことであり、Ａｇ−酸化物合金板の断面比率で９０％以下の範囲のことをいう。 In the Ag-oxide alloy listed as a comparative example as a conventional example, the oxide dilute layer is a time passage by forming an internal oxide layer by subjecting an Ag-Cu alloy having a desired composition to an internal oxidation treatment for a long time. As a result, there is no unoxidized layer in which no oxide is deposited, Cu is almost lost as a solute element previously contained in Ag as an Ag-Cu alloy, and a layer in which oxide is formed thinly in the center of the material. I mean. The definition of the diluted oxide layer in the comparative example is a layer having an oxide concentration lower than about 1% by mass, and means a range of 10% or less in terms of the cross-sectional ratio of the Ag-oxide alloy plate. . In addition, the definition of the unoxidized layer in the present invention is a layer that does not contain an oxide, apart from the internal oxide layer, and the cross-sectional ratio of the Ag-oxide alloy plate is 90% or less. Say.
溶質元素が未酸化層から表層に向かって拡散する過程においては、上記拡散合金化層中にＳｎ、Ｉｎ、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阻害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 process in which the solute element diffuses from the unoxidized layer toward the surface layer, the concentration gradient is obtained by adding at least one selected from the group of Sn, In, Fe, Ni, and Co into the diffusion alloyed layer. As a result, the oxide structure is refined by inhibiting the aggregation due to the movement of the precipitated oxide, and a uniform dispersion can be obtained. Furthermore, it becomes a complex oxide with Cu, for example, (Cu-Sn) Ox, and has an effect of improving the welding resistance.
ここで、上記拡散合金化層において、Ｓｎ、Ｉｎ、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％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。また、金属層としてＳｎ、Ｉｎ、Ｆｅ、ＮｉおよびＣｏの群から選ばれた１種以上の金属層を少なくとも１層積層させ、かつ、構成成分の一部を隣接する金属層へ拡散および合金化させて拡散合金化層を形成する場合には、前記理由により、拡散合金化層の溶質元素の含有率が０．０１〜５質量％の範囲に収まるように、積層する各金属層の層厚、内部酸化処理の条件および熱処理の条件を調整することが好ましい。 Here, in the diffusion alloyed layer, the reason why at least one selected from the group of Sn, In, Fe, Ni, and Co is 0.01 to 5% by mass is less than 0.01% by mass. This is because the movement of the solute element during the internal oxidation treatment cannot be sufficiently suppressed, and a uniform dispersion of the oxide cannot be obtained. If the amount exceeds 5% by mass, a coarse oxide is formed at the grain boundary and the contact resistance. This is to cause a rise in In addition, at least one metal layer selected from the group consisting of Sn, In, Fe, Ni and Co is laminated as a metal layer, and a part of the constituent components are diffused and alloyed to the adjacent metal layer. In the case of forming a diffusion alloyed layer, the thickness of each metal layer to be laminated so that the content of the solute element in the diffusion alloyed layer falls within the range of 0.01 to 5% by mass for the reason described above. It is preferable to adjust the conditions for the internal oxidation treatment and the conditions for the heat treatment.
本発明は、上記内部酸化処理において、多層構造材の表裏両面の拡散合金化層の表層もしくは片面の表層のみ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。これによって拡散合金化層の表層に内部酸化層、材料中層部に未酸化層、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 the internal oxidation treatment, only the surface layer of the diffusion alloyed layer on both the front and back surfaces of the multilayer structure material or only the surface layer on one surface has an internal oxidized structure, and the internal oxidation conditions for this are desired. The thickness is adjusted in the internal oxidation furnace under conditions of 500 ° C. to 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 surface layer of the diffusion alloyed layer, an unoxidized layer can be formed on the middle layer portion of the material, and a substrate layer can be formed on the central portion of the material. The average particle diameter of the oxide particles dispersed in the internal oxide layer is 0.5 to 5 μm, preferably 1 to 4 μm, and 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５００℃〜７５０℃が好ましい。５００℃より低いと十分に酸化反応が進まず、一方、７５０℃より高温であると、酸化物希薄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. 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 diluted 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、保護層の有無、金属層の組成、拡散合金化層の組成、多層構造材の板厚、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 internal oxidation treatment is the target internal oxide layer thickness, unoxidized layer thickness, presence or absence of protective layer, metal layer composition, diffusion alloyed layer composition, multilayer structure material thickness, as described above. It is necessary to appropriately adjust the temperature and the oxygen partial pressure during internal oxidation.
内部酸化処理の時間は、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。しかしながら、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、基板層に対する金属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。また、保護層を基板の表裏両面に形成させた場合には、内部酸化処理時の基板への酸素の侵入を妨げ、内部酸化層が基板から剥離するのを防止する効果がある。 The time for the internal oxidation treatment is preferably 0.25 hours or longer, although it depends on the target internal oxide layer thickness. 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, since the internal oxidation of the substrate layer may cause peeling of each layer, the ratio of the thickness of the metal layer to the substrate layer is increased or the plate of the multi-layer structure material so that the internal oxidation treatment is not performed on the substrate layer. It is necessary to insert an internal oxidation treatment in a thick state. In addition, when the protective layers are formed on both the front and back surfaces of the substrate, there is an effect of preventing oxygen from entering the substrate during the internal oxidation treatment and preventing the internal oxide layer from peeling from the substrate.
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いため、内部酸化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 use application of the thermal fuse, but a thin plate material of 0.1 mm or less is used because of the mechanism of the thermal fuse. However, since it is difficult to uniformly perform the internal oxidation treatment on the thin plate material, it is necessary to thin the material after the internal oxidation 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、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、各種層の層厚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 made of Cu or Cu alloy with high workability at the center of the electrode material, the internal oxide layer It was possible to greatly improve the rolling processability without reducing the oxide content, and succeeded in rolling with a cross-section reduction rate of 80% or more. Furthermore, by providing a substrate layer rich in processability, it becomes possible to improve the processability of various other layers that are relatively inferior in processability with a single layer. While maintaining the structure, it was successfully rolled into a sheet material of 0.1 mm or less.
本発明の電極材料によると、金属層もしくは拡散合金化層の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, the content of Ag is decreased by increasing the Cu content in the metal layer or diffusion alloyed layer to 50% by mass and increasing the oxide content after the internal oxidation treatment. However, 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、電極材料中心部にＣｕを主成分とする基板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, by providing a substrate mainly composed of Cu at the center of the electrode material, workability can be greatly improved without reducing the oxide content of the internal oxide layer. Is possible. 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、保護層を設けることで、従来の製造方法では不可能であった薄板への内部酸化処理が可能になり、かつめっき法および拡散合金化処理を用いることにより、平滑で均一な内部酸化層を形成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。 Furthermore, by providing a protective layer, it becomes possible to internally oxidize thin plates, which was impossible with conventional manufacturing methods, and by using a plating method and diffusion alloying treatment, a smooth and uniform internal oxide layer can be obtained. It becomes possible to provide an electrode material for a thermal fuse in which is formed.
また、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。 In addition, while maintaining various characteristics such as welding resistance and low contact resistance required for a thermal fuse electrode material, the amount of Ag and the like used can be greatly reduced, and an inexpensive thermal fuse electrode material is provided. It becomes possible.
本発明の実施例を表１〜５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２に対応する形式で表３を、表４に対応する形式で表５を示す。 The Example of this invention is shown to Tables 1-5, and the manufacturing method of these electrode materials for thermal fuses is demonstrated. In addition, an Example and a comparative example are electrode material kind No .. Table 3 is shown in a format corresponding to Table 2, and Table 5 is shown in a format corresponding to Table 4.
具体的には、本発明の製造方法１〜６の各々の金属層を積層するにあたってのめっき条件を表１に、本発明の製造方法１〜６の拡散合金化層もしくは保護層の成分組成を表２もしくは表４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２および表４に併記する。表２もしくは表４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３もしくは表５に記載する。表２〜５に記載の各項目の評価方法として、Ａｇ−Ｃｕ合金板、拡散合金化層および保護層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った。Ａｇ−Ｃｕ合金板および拡散合金化層において、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。また、保護層の主成分組成が１種のみである場合にはその主成分元素および不可避不純物を○と記載し、保護層の主成分組成が２種以上である場合にはその内の１種および不可避不純物を残と記載した。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 plating conditions for laminating each metal layer of the production methods 1 to 6 of the present invention are shown in Table 1, and the component composition of the diffusion alloyed layer or protective layer of the production methods 1 to 6 of the present invention is shown in Table 1. It is described in Table 2 or Table 4. Moreover, the component composition contained in the Ag-Cu alloy plate of a comparative example is written together in Table 2 and Table 4. In the form corresponding to Table 2 or Table 4, internal oxidation temperature, internal oxidation time, oxygen partial pressure, average particle diameter of oxide, workability of rolling after internal oxidation treatment, final thickness of electrode material for thermal fuse The final processing rate is shown in Table 3 or Table 5. As an evaluation method of each item of Tables 2-5, the component composition contained in an Ag-Cu alloy plate, a diffusion alloying layer, and a protective layer is quantitatively analyzed using a wavelength dispersive electron microscope and an ICP emission analyzer. went. In the Ag-Cu alloy sheet and the diffusion alloyed layer, the remaining Ag and unavoidable impurities of the component composition were described as remaining. In addition, when the protective layer has only one main component composition, the main component element and inevitable impurities are described as ◯, and when the protective layer has two or more main component compositions, one of them And the inevitable impurities were described as the balance. 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.
なお、製造方法１〜６で得られた多層構造材２の拡散合金化層もしくは保護層９は、波長分散型電子顕微鏡を用いて各多層構造材の断面を分析し、本発明の電極材料種類Ｎｏ．１〜４０のいずれにおいても各々の金属層が相互に拡散した濃度勾配の無い所望組成の拡散合金化層５および保護層９の存在が確認できた。 In addition, the diffusion alloying layer or protective layer 9 of the multilayer structure material 2 obtained by the manufacturing methods 1 to 6 analyzes the cross section of each multilayer structure material using a wavelength dispersive electron microscope, and the electrode material type of the present invention No. In any of 1 to 40, the presence of the diffusion alloying layer 5 and the protective layer 9 having a desired composition without concentration gradient in which the respective metal layers diffused to each other was confirmed.
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１〜３では基板層に無酸素Ｃｕを用い、製造方法４〜６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 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 to 3, oxygen-free Cu was used for the substrate layer, and in manufacturing methods 4 to 6 a Cu alloy was used for the substrate layer, but no difference was found in workability.
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７および中層部に酸化物希薄層１０を形成したＡｇ−酸化物合金板（図１０）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２〜５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. 10) in which an inner oxide layer 7 containing an oxide on both surface layers and an oxide thin layer 10 in the middle layer portion were formed, and after final annealing, a final plate 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 2 to 5. The reason why the internal oxidation time of the comparative example was unified to 48 hours is that the oxide thin layer can be reliably 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 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 is It means a layer in the range of 10% or less.
以下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２および表４に示す。無酸素Ｃｕを溶解法で作製し、さらにこれに押出加工および圧延加工を施し、幅：６０ｍｍ、板厚：０．３ｍｍ、長さ５０ｍの寸法を有する条材形状の基板とした。これに表面研磨加工および化学研磨により表面処理を行い、脱脂洗浄処理を施した。The production method of the present invention will be described below.
Manufacturing method 1
Examples according to this production method are shown in Tables 2 and 4. Oxygen-free Cu was produced by a melting method, and further subjected to extrusion and rolling to obtain a strip-shaped substrate having dimensions of width: 60 mm, plate thickness: 0.3 mm, and length of 50 m. This was subjected to surface treatment by surface polishing and chemical polishing, and then subjected to degreasing cleaning treatment.
次に、めっき浴中を連続的に通過させる電解めっき法により、１種以上のＡｇ合金、１種以上のＣｕ合金、Ａｇ、Ｃｕ、Ｓｎ、Ｉｎ、Ｔｉ、Ｆｅ、ＮｉおよびＣｏの群から選ばれた少なくとも１種以上の金属層を基板の長手方向の表裏両面もしくは片面に対して少なくとも１層以上積層させて、基板層１の長手方向の表裏両面に単層金属層３もしくは多層金属層４を有する多層構造材２を作製した。 Next, it is selected from the group of one or more Ag alloys, one or more Cu alloys, Ag, Cu, Sn, In, Ti, Fe, Ni, and Co by an electrolytic plating method that continuously passes through the plating bath. At least one or more kinds of the metal layers are laminated on the front and back surfaces or one side in the longitudinal direction of the substrate, and the single layer metal layer 3 or the multilayer metal layer 4 is formed on both the front and back surfaces in the longitudinal direction of the substrate layer 1. A multilayer structural material 2 having
基板に積層する金属層の層数および積層順は、単層金属層３においてはＡｇ合金を１層積層させた。多層金属層４においては最大の積層数は９層までとし、積層順は、１種以上のＡｇ合金、１種以上のＣｕ合金、Ａｇ、Ｃｕ、Ｓｎ、Ｉｎ、Ｔｉ、Ｆｅ、ＮｉおよびＣｏの群から選ばれた少なくとも２種以上の金属層を多層にして積層させ、積層させる金属層と隣接する他の金属層が異種金属になるようにする。なお、多層構造材２の最表面には、Ｓｎ、Ｉｎ、Ｔｉ、Ｆｅ、Ｎｉ、Ｃｏ、Ｃｕ、もしくはＣｕ合金は積層しない（図１および図２）。 Regarding the number of metal layers to be laminated on the substrate and the order of lamination, in the single-layer metal layer 3, one Ag alloy was laminated. In the multilayer metal layer 4, the maximum number of stacks is up to 9, and the stacking order is one or more Ag alloys, one or more Cu alloys, Ag, Cu, Sn, In, Ti, Fe, Ni, and Co. At least two or more kinds of metal layers selected from the group are laminated in a multilayer so that the metal layer to be laminated and another metal layer adjacent to the metal layer are different metals. Note that Sn, In, Ti, Fe, Ni, Co, Cu, or a Cu alloy is not laminated on the outermost surface of the multilayer structural material 2 (FIGS. 1 and 2).
なお、本製造方法では、多層構造材の板厚を０．５ｍｍとした。 In this manufacturing method, the thickness of the multilayer structure material was set to 0.5 mm.
各々の金属層を積層するにあたってのめっき条件を表１に示す。めっき条件は本実施形態に限定されることはなく、適宜設定することができる。めっき条件は、めっきの密着性に及ぼす影響が大きいので、下地となる金属層や基板の材質によって使い分けた。また、めっき浴組成、めっき時間、めっき浴温度および電流密度は、目的とする金属層の層厚によって適宜変化させた。なお、基板層１の長手方向の表裏両面において、金属層の層厚や組成が表裏非対称であっても良い。 Table 1 shows the plating conditions for laminating each metal layer. The plating conditions are not limited to this embodiment, and can be set as appropriate. Since the plating conditions have a great influence on the adhesion of plating, the plating conditions were selected according to the metal layer used as a base and the material of the substrate. The plating bath composition, plating time, plating bath temperature, and current density were appropriately changed depending on the target metal layer thickness. It should be noted that the thickness and composition of the metal layer may be asymmetric on the front and back surfaces of the substrate layer 1 in the longitudinal direction.
つぎに、多層構造材２に熱処理を施すことにより、単層金属層３および多層金属層４を基板層１に定着させ、かつ試験条件を揃える為に完全焼鈍を施した。さらに、この熱処理時に金属層を隣接する他の層へ拡散および合金化させて、電極材料種類Ｎｏ.１〜４０に当該する所望の各組成の拡散合金化層５を形成した（図３）。 Next, heat treatment was performed on the multilayer structural material 2 to fix the single-layer metal layer 3 and the multilayer metal layer 4 to the substrate layer 1, and complete annealing was performed in order to align the test conditions. Further, during this heat treatment, the metal layer was diffused and alloyed to other adjacent layers to form a diffusion alloyed layer 5 having each desired composition corresponding to the electrode material types No. 1 to 40 (FIG. 3).
その後、多層構造材２の表裏両面に表面研磨加工および脱脂洗浄処理を施し、内部酸化炉中で５００℃〜７５０℃、０．２５時間以上、酸素分圧０．１〜２ＭＰａの条件で内部酸化処理を行った。この際、金属層の組成および層厚により上記各範囲内で条件を選択し、多層構造材２の表裏両面の表層に酸化物６を含有する内部酸化層７を形成し、中層部に未酸化層８、材料中心部に基板層１を持つ多層構造を有するようにした（図４）。 Thereafter, both the front and back surfaces of the multilayer structural material 2 are subjected to surface polishing processing and degreasing cleaning treatment, and internal oxidation is performed in an internal oxidation furnace at 500 ° C. to 750 ° C. for 0.25 hours or more and an oxygen partial pressure of 0.1 to 2 MPa. Processed. At this time, conditions are selected within the above ranges depending on the composition and layer thickness of the metal layer, the internal oxide layer 7 containing the oxide 6 is formed on the front and back surfaces of the multilayer structural material 2, and the non-oxidized layer is formed on the middle layer portion. Layer 8 has a multilayer structure with substrate layer 1 in the center of the material (FIG. 4).
つぎに、上記多層構造を有したまま、図４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, cold rolling was performed with the multilayer structure shown in FIG. 4 while having the multilayer structure, and the final plate thickness was processed to 0.1 mm or less to produce a thermal fuse electrode material. .
製造方法２
本製造方法による実施例を表２および表４に示す。無酸素Ｃｕを溶解法で作製し、さらにこれに押出加工および圧延加工を施し、幅：６０ｍｍ、板厚：０．３ｍｍ、長さ５０ｍの寸法を有する条材形状の基板とした。これに表面研磨加工および化学研磨により表面処理を行い、脱脂洗浄処理を施した。Manufacturing method 2
Examples according to this production method are shown in Tables 2 and 4. Oxygen-free Cu was produced by a melting method, and further subjected to extrusion and rolling to obtain a strip-shaped substrate having dimensions of width: 60 mm, plate thickness: 0.3 mm, and length of 50 m. This was subjected to surface treatment by surface polishing and chemical polishing, and then subjected to degreasing cleaning treatment.
つぎに、めっき浴中を連続的に通過させる電解めっき法により、Ｓｎ、Ｉｎ、Ｔｉ、Ｆｅ、ＮｉおよびＣｏの群から選ばれた少なくとも１種以上の金属層を保護層９として基板の長手方向の表裏両面に対して少なくとも１層以上積層させた後、単層金属層３もしくは多層金属層４を長手方向の表裏両面に対して積層させて、板厚０．５ｍｍの多層構造材２（図５および図６）を作製した。基板に積層する金属層の層数および積層順は、単層金属層３もしくは多層金属層４において、製造方法１と同様とした。 Next, in the longitudinal direction of the substrate, at least one metal layer selected from the group of Sn, In, Ti, Fe, Ni, and Co is used as a protective layer 9 by an electrolytic plating method that continuously passes through the plating bath. After laminating at least one or more layers on both front and back surfaces, a single-layer metal layer 3 or a multilayer metal layer 4 is laminated on both front and back surfaces in the longitudinal direction to form a multilayer structure material 2 having a thickness of 0.5 mm (see FIG. 5 and FIG. 6) were produced. The number of metal layers to be laminated on the substrate and the order of lamination were the same as those in the manufacturing method 1 in the single-layer metal layer 3 or the multilayer metal layer 4.
次に、多層構造材２に熱処理を施すことにより、保護層９、単層金属層３および多層金属層４を基板に定着させ、かつ試験条件を揃える為に完全焼鈍を施した。さらに、この熱処理時に金属層を隣接する他の金属層へ拡散および合金化させて、電極材料種類Ｎｏ.１〜４０に当該する所望の各組成の拡散合金化層５を形成した（図７）。 Next, the protective layer 9, the single layer metal layer 3, and the multilayer metal layer 4 were fixed to the substrate by heat-treating the multilayer structural material 2, and complete annealing was performed in order to align the test conditions. Further, during this heat treatment, the metal layer was diffused and alloyed to other adjacent metal layers to form the diffusion alloyed layer 5 having each desired composition corresponding to the electrode material types No. 1 to 40 (FIG. 7). .
前記以外の工程を上記の製造方法１と同様にして、多層構造材２の両面の表層に酸化物６を含有する内部酸化層７を形成し、中層部に未酸化層８および保護層９、材料中心部に基板層１を持つ多層構造を有する、温度ヒューズ用電極材料（図８）を作製した。 The steps other than the above are performed in the same manner as in the manufacturing method 1 described above, so that the internal oxide layer 7 containing the oxide 6 is formed on both surface layers of the multilayer structural material 2, and the unoxidized layer 8 and the protective layer 9 are formed in the middle layer portion. A temperature fuse electrode material (FIG. 8) having a multilayer structure having a substrate layer 1 at the center of the material was produced.
製造方法３
本製造方法による実施例を表２および表４に示す。無酸素Ｃｕを溶解法で作製し、さらにこれに押出加工および圧延加工を施し、幅：６０ｍｍ、板厚：０．３ｍｍ、長さ５０ｍの寸法を有する条材形状の基板とした。これに表面研磨加工および化学研磨により表面処理を行い、脱脂洗浄処理を施した。Manufacturing method 3
Examples according to this production method are shown in Tables 2 and 4. Oxygen-free Cu was produced by a melting method, and further subjected to extrusion and rolling to obtain a strip-shaped substrate having dimensions of width: 60 mm, plate thickness: 0.3 mm, and length of 50 m. This was subjected to surface treatment by surface polishing and chemical polishing, and then subjected to degreasing cleaning treatment.
つぎに、めっき浴中を連続的に通過させる電解めっき法により、Ｓｎ、Ｉｎ、Ｔｉ、Ｆｅ、Ｎｉ、およびＣｏの群から選ばれた少なくとも１種以上の金属層を保護層９として基板の長手方向の表裏両面に対して少なくとも１層以上積層させた後、さらに長手方向の片方の面には単層金属層３としてＡｇを、長手方向の反対側の面には多層金属層４を積層させて、板厚０．５ｍｍの多層構造材２を作製した(図１１)。基板に積層する金属層の層数および積層順は、多層金属層４おいて、製造方法１と同様とした。 Next, the longitudinal direction of the substrate is formed by using at least one metal layer selected from the group consisting of Sn, In, Ti, Fe, Ni, and Co as a protective layer 9 by an electrolytic plating method that continuously passes through the plating bath. After laminating at least one layer on both front and back surfaces in the direction, Ag is further laminated as a single-layer metal layer 3 on one side in the longitudinal direction, and a multilayer metal layer 4 is laminated on the opposite side in the longitudinal direction. Thus, a multilayer structural member 2 having a thickness of 0.5 mm was produced (FIG. 11). The number of metal layers to be laminated on the substrate and the order of lamination were the same as those in the manufacturing method 1 in the multilayer metal layer 4.
つぎに、多層構造材２に熱処理を施すことにより、保護層９、単層金属層３および多層金属層４を基板に定着させ、かつ試験条件を揃える為に完全焼鈍を施した。さらに、多層金属層４において、この熱処理時に金属層を隣接する他の金属層へ拡散および合金化させて、電極材料種類Ｎｏ.１〜４０に当該する所望の各組成の拡散合金化層５を形成した（図１２）。 Next, the protective layer 9, the single layer metal layer 3 and the multilayer metal layer 4 were fixed to the substrate by heat-treating the multilayer structural material 2, and complete annealing was performed in order to align the test conditions. Furthermore, in the multi-layer metal layer 4, the metal layer is diffused and alloyed to other adjacent metal layers during the heat treatment, and the diffusion alloyed layer 5 having each desired composition corresponding to the electrode material types No. 1 to 40 is obtained. Formed (FIG. 12).
前記以外の工程を上記の製造方法１と同様にして、多層構造材２の片方の面の表層に酸化物６を含有する内部酸化層７を形成し、中層部に未酸化層８および保護層９、材料中心部に基板層１を持つ多層構造を有し、さらに反対側の面には単層金属層３および保護層９を有する温度ヒューズ用電極材料（図９）を作製した。 The other steps are the same as in manufacturing method 1 described above, and the internal oxide layer 7 containing the oxide 6 is formed on the surface layer on one side of the multilayer structure 2, and the unoxidized layer 8 and the protective layer are formed in the middle layer portion. 9. A thermal fuse electrode material (FIG. 9) having a multilayer structure having a substrate layer 1 at the center of the material and having a single-layer metal layer 3 and a protective layer 9 on the opposite surface was prepared.
製造方法４
本製造方法による実施例を表４および表５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、幅：６０ｍｍ、板厚：０．３ｍｍ、長さ５０ｍの寸法を有する条材形状の基板とした。これに表面研磨加工および化学研磨により表面処理を行い、脱脂洗浄処理を施した。Manufacturing method 4
Examples according to this production method are shown in Tables 4 and 5. 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 strip-shaped substrate having dimensions of width: 60 mm, plate thickness: 0.3 mm, and length of 50 m. This was subjected to surface treatment by surface polishing and chemical polishing, and then subjected to degreasing cleaning treatment.
つぎに、無酸素Ｃｕを上記Ｃｕ合金からなる基板に置き換えた以外は製造方法１と同様にして、図４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 temperature having the multilayer structure shown in FIG. 4 and a final plate thickness of 0.1 mm or less is obtained in the same manner as in manufacturing method 1 except that oxygen-free Cu is replaced with the substrate made of the Cu alloy. A fuse electrode material was prepared.
製造方法５
本製造方法による実施例を表４および表５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、幅：６０ｍｍ、板厚：０．３ｍｍ、長さ５０ｍの寸法を有する条材形状の基板とした。これに表面研磨加工および化学研磨により表面処理を行い、脱脂洗浄処理を施した。Manufacturing method 5
Examples according to this production method are shown in Tables 4 and 5. 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 strip-shaped substrate having dimensions of width: 60 mm, plate thickness: 0.3 mm, and length of 50 m. This was subjected to surface treatment by surface polishing and chemical polishing, and then subjected to degreasing cleaning treatment.
つぎに、無酸素Ｃｕを上記Ｃｕ合金からなる基板に置き換えた以外は製造方法２と同様にして、図８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 temperature having the multilayer structure shown in FIG. 8 and a final plate thickness of 0.1 mm or less is obtained in the same manner as in manufacturing method 2 except that oxygen-free Cu is replaced with the substrate made of the Cu alloy. A fuse electrode material was prepared.
製造方法６
本製造方法による実施例を表４および表５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、幅：６０ｍｍ、板厚：０．３ｍｍ、長さ５０ｍの寸法を有する条材形状の基板とした。これに表面研磨加工および化学研磨により表面処理を行い、脱脂洗浄処理を施した。Manufacturing method 6
Examples according to this production method are shown in Tables 4 and 5. 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 strip-shaped substrate having dimensions of width: 60 mm, plate thickness: 0.3 mm, and length of 50 m. This was subjected to surface treatment by surface polishing and chemical polishing, and then subjected to degreasing cleaning treatment.
つぎに、無酸素Ｃｕを上記Ｃｕ合金からなる基板に置き換えた以外は製造方法３と同様にして、図９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 temperature having the multilayer structure shown in FIG. 9 and a final plate thickness of 0.1 mm or less is obtained in the same manner as in manufacturing method 3 except that oxygen-free Cu is replaced with the substrate made of the Cu alloy. A fuse electrode material was prepared.
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、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３および表５に示す。 Therefore, the temperature 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, and the movable electrode is subjected to a temperature sensitive pellet type temperature. Tables 3 and 5 show the results of conducting an energization test and a current interruption test with a fuse mounted, DC30V, 20A, and a temperature rising 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。
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、昇温速度１℃毎分、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 energization test, the temperature fuse was energized for 10 minutes, and the temperature difference on the surface of the metal case of the temperature fuse before and after the test was less than 10 ° C., and the temperature difference of 10 ° C. or more was evaluated as x.
In the current interruption test, the temperature fuse is energized for 10 minutes, and then the temperature of the test environment is raised to a temperature 10 ° C higher than the operating temperature at a heating rate of 1 ° C per minute while energization continues. I tried to cut off the current. 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 基板層
２ 多層構造材
３ 単層金属層
４ 多層金属層
５ 拡散合金化層
６ 酸化物
７ 内部酸化層
８ 未酸化層
９ 保護層
１０ 酸化物希薄層DESCRIPTION OF SYMBOLS 1 Substrate layer 2 Multilayer structure material 3 Single layer metal layer 4 Multilayer metal layer 5 Diffusion alloying layer 6 Oxide 7 Internal oxide layer 8 Unoxidized layer 9 Protective layer 10 Oxide diluted layer
以下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２および表３に示す。無酸素Ｃｕを溶解法で作製し、さらにこれに押出加工および圧延加工を施し、幅：６０ｍｍ、板厚：０．３ｍｍ、長さ５０ｍの寸法を有する条材形状の基板とした。これに表面研磨加工および化学研磨により表面処理を行い、脱脂洗浄処理を施した。
The production method of the present invention will be described below.
Manufacturing method 1
Examples according to the production method are shown in Tables 2 and 3 . Oxygen-free Cu was produced by a melting method, and further subjected to extrusion and rolling to obtain a strip-shaped substrate having dimensions of width: 60 mm, plate thickness: 0.3 mm, and length of 50 m. This was subjected to surface treatment by surface polishing and chemical polishing, and then subjected to degreasing cleaning treatment.
製造方法２
本製造方法による実施例を表２および表３に示す。無酸素Ｃｕを溶解法で作製し、さらにこれに押出加工および圧延加工を施し、幅：６０ｍｍ、板厚：０．３ｍｍ、長さ５０ｍの寸法を有する条材形状の基板とした。これに表面研磨加工および化学研磨により表面処理を行い、脱脂洗浄処理を施した。
Manufacturing method 2
Examples according to the production method are shown in Tables 2 and 3 . Oxygen-free Cu was produced by a melting method, and further subjected to extrusion and rolling to obtain a strip-shaped substrate having dimensions of width: 60 mm, plate thickness: 0.3 mm, and length of 50 m. This was subjected to surface treatment by surface polishing and chemical polishing, and then subjected to degreasing cleaning treatment.
製造方法３
本製造方法による実施例を表２および表３に示す。無酸素Ｃｕを溶解法で作製し、さらにこれに押出加工および圧延加工を施し、幅：６０ｍｍ、板厚：０．３ｍｍ、長さ５０ｍの寸法を有する条材形状の基板とした。これに表面研磨加工および化学研磨により表面処理を行い、脱脂洗浄処理を施した。
Manufacturing method 3
Examples according to the production method are shown in Tables 2 and 3 . Oxygen-free Cu was produced by a melting method, and further subjected to extrusion and rolling to obtain a strip-shaped substrate having dimensions of width: 60 mm, plate thickness: 0.3 mm, and length of 50 m. This was subjected to surface treatment by surface polishing and chemical polishing, and then subjected to degreasing cleaning treatment.
Claims (10)
可動電極の材料として、基板層となる基板の表裏両面に対して、１種以上のＡｇ合金の金属層を少なくとも１層以上積層した多層構造材とし、この多層構造材に内部酸化処理を施して多層構造材の表裏両面の少なくとも片面の表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, a multilayer structure material in which at least one metal layer of one or more Ag alloys is laminated on both the front and back surfaces of the substrate to be a substrate layer is subjected to internal oxidation treatment. An electrode material for a thermal fuse, characterized in that it has a multilayer structure in which an internal oxide layer is formed on at least one surface layer of both surfaces of the multilayer structure material.
可動電極の材料として、基板層となる基板に対して、基板の少なくとも片面の最表層には１種以上のＡｇ合金の金属層を積層させ、かつ基板の少なくとも片面には１種以上のＡｇ合金、１種以上のＣｕ合金、Ａｇ、Ｃｕ、Ｓｎ、Ｉｎ、Ｔｉ、Ｆｅ、Ｎｉ、およびＣｏの群から選ばれた少なくとも１種以上の金属層を少なくとも２層以上積層した多層構造材とし、この多層構造材を熱処理により前記金属層の少なくとも１層の構成成分の一部もしくはその全てが隣接する他の金属層へ拡散および合金化させて拡散合金化層が形成され、この多層構造材に内部酸化処理を施して多層構造材の表裏両面の少なくとも片面の表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, one or more Ag alloy metal layers are laminated on at least one surface of the substrate, and one or more Ag alloys are formed on at least one surface of the substrate. A multi-layer structure material in which at least one or more metal layers selected from the group of one or more kinds of Cu alloys, Ag, Cu, Sn, In, Ti, Fe, Ni, and Co are laminated, A diffusion alloyed layer is formed by diffusing and alloying a multilayer structure material by heat treatment with a part or all of the constituent components of at least one layer of the metal layer to another adjacent metal layer. An electrode material for a thermal fuse, characterized by having a multilayer structure in which an internal oxide layer is formed on at least one surface of the front and back surfaces of the multilayer structure material by oxidation treatment.
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| PCT/JP2012/082578 WO2014091631A1 (en) | 2012-12-14 | 2012-12-14 | Electrode material for thermal fuse and production method therefor |
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|---|---|---|---|---|
| JPS62241211A (en) * | 1986-04-11 | 1987-10-21 | 中外電気工業株式会社 | Spot-weldable tape electric contact material |
| JPH025844U (en) * | 1988-06-24 | 1990-01-16 | ||
| WO2003009323A1 (en) * | 2001-07-18 | 2003-01-30 | Nec Schott Components Corporation | Thermal fuse |
| JP2007291510A (en) * | 2006-03-28 | 2007-11-08 | Furukawa Electric Co Ltd:The | Silver coated composite material for movable contact and method for producing the same |
| JP2011137198A (en) * | 2009-12-28 | 2011-07-14 | Tokuriki Honten Co Ltd | Electrode material and method for manufacturing the same |
| WO2013005801A1 (en) * | 2011-07-06 | 2013-01-10 | 株式会社徳力本店 | Electrode material for thermal fuses, manufacturing process therefor and thermal fuses using said electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62241211A (en) * | 1986-04-11 | 1987-10-21 | 中外電気工業株式会社 | Spot-weldable tape electric contact material |
| JPH025844U (en) * | 1988-06-24 | 1990-01-16 | ||
| WO2003009323A1 (en) * | 2001-07-18 | 2003-01-30 | Nec Schott Components Corporation | Thermal fuse |
| JP2007291510A (en) * | 2006-03-28 | 2007-11-08 | Furukawa Electric Co Ltd:The | Silver coated composite material for movable contact and method for producing the same |
| JP2011137198A (en) * | 2009-12-28 | 2011-07-14 | Tokuriki Honten Co Ltd | Electrode material and method for manufacturing the same |
| WO2013005801A1 (en) * | 2011-07-06 | 2013-01-10 | 株式会社徳力本店 | Electrode material for thermal fuses, manufacturing process therefor and thermal fuses using said electrode material |
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