JP7024358B2 - Manufacturing method of copper terminal material - Google Patents

Manufacturing method of copper terminal material Download PDF

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JP7024358B2
JP7024358B2 JP2017229793A JP2017229793A JP7024358B2 JP 7024358 B2 JP7024358 B2 JP 7024358B2 JP 2017229793 A JP2017229793 A JP 2017229793A JP 2017229793 A JP2017229793 A JP 2017229793A JP 7024358 B2 JP7024358 B2 JP 7024358B2
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隆二 植杉
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Mitsubishi Materials Corp
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Description

本発明は、自動車や民生機器等の電気配線の接続に使用されるコネクタ用端子として有用な白金、パラジウム等の貴金属を含有する被膜が設けられた銅端子材の製造方法に関する。 The present invention relates to a method for manufacturing a copper terminal material provided with a coating containing a precious metal such as platinum or palladium, which is useful as a terminal for a connector used for connecting electrical wiring of an automobile or a consumer device.

従来、自動車や民生機器などの電気配線の接続に用いられるコネクタ用端子が知られている。このようなコネクタ用端子として用いられる端子材として、銅又は銅合金基材の表面にニッケルやコバルト等の金属により構成されるめっき層が下地層として形成され、該下地層の上面に錫等の金属メッキ層が形成された端子材が開示されている（例えば、特許文献１参照）。
この特許文献１に記載の端子材では、ニッケルやコバルト等のめっき層が銅又は銅合金基材の表面に形成されていることから、表面に位置する錫等の金属メッキ層に銅又は銅合金基材の銅成分が拡散することを抑制している。 Conventionally, connector terminals used for connecting electrical wiring of automobiles and consumer devices are known. As a terminal material used as a terminal for such a connector, a plating layer made of a metal such as nickel or cobalt is formed as an underlayer on the surface of a copper or copper alloy base material, and tin or the like is formed on the upper surface of the underlayer. A terminal material on which a metal plating layer is formed is disclosed (see, for example, Patent Document 1).
In the terminal material described in Patent Document 1, since a plating layer such as nickel or cobalt is formed on the surface of a copper or copper alloy base material, copper or a copper alloy is formed on a metal plating layer such as tin located on the surface. It suppresses the diffusion of the copper component of the base material.

また、端子材の接点箇所の信頼性を向上させるため、金や銀等の貴金属を接点箇所に部分めっきする方法が提案されている（例えば、特許文献２参照）。 Further, in order to improve the reliability of the contact points of the terminal material, a method of partially plating the contact points with a precious metal such as gold or silver has been proposed (see, for example, Patent Document 2).

特開平８－７９６０号公報Japanese Unexamined Patent Publication No. 8-7960 特開２０００－８７２８９号公報Japanese Unexamined Patent Publication No. 2000-87289

しかしながら、特許文献１に記載の端子材では、ニッケルやコバルトなどの下地層を形成しているので、工程が煩雑である。この下地層はめっき法を用いて形成されることから、めっき廃液の処理が必要であること等、環境負荷の低減への対策が必要となる。また、特許文献２に記載の部分めっき方法では、金や銀等の貴金属を接点箇所に部分めっきする際にマスキングなどの工程や装置が複雑になる他、シアン等の毒物の使用や廃液の処理が必要になる等、環境負荷の低減への対策が必要となる。 However, in the terminal material described in Patent Document 1, since a base layer such as nickel or cobalt is formed, the process is complicated. Since this base layer is formed by using a plating method, it is necessary to take measures to reduce the environmental load, such as the need to treat the plating waste liquid. Further, in the partial plating method described in Patent Document 2, processes and devices such as masking are complicated when a precious metal such as gold or silver is partially plated at a contact point, and poisonous substances such as cyanide are used and waste liquid is treated. It is necessary to take measures to reduce the environmental load, such as the need for.

本発明は、このような事情に鑑みてなされたもので、銅又は銅合金からなる端子材の被膜形成において廃液等の処理を不要にできる銅端子材の製造方法を提供することを目的とする。 The present invention has been made in view of such circumstances, and an object of the present invention is to provide a method for manufacturing a copper terminal material, which can eliminate the need for treatment of waste liquid or the like in forming a film of a terminal material made of copper or a copper alloy. ..

本発明の銅端子材は、銅又は銅合金からなる基材の表面の一部に、金及び銀の少なくとも一種と、白金及びパラジウムの少なくとも一種とを含む焼成層が形成されている。 In the copper terminal material of the present invention, a fired layer containing at least one of gold and silver and at least one of platinum and palladium is formed on a part of the surface of a base material made of copper or a copper alloy.

本発明では、焼成層に白金及びパラジウムの少なくとも一種を含むので、基材の銅成分が焼成層に拡散することを抑制できる。また、焼成層は、金又は銀の少なくとも一種を含むので、銅端子材がコネクタとして用いられる場合に、接点箇所の接触抵抗を低減させることができ、接点信頼性を高めることができる。したがって、銅又は銅合金からなる基材の表面に下地層及び貴金属層の２層を形成する従来の構成に比べて、基材の表面の一部に焼成層を１層形成するだけの簡単な構成で、銅成分の拡散を抑制し、かつ接点信頼性を高めることができる。また、めっき法を用いることなく被膜を形成できるので、めっき法を用いて下地層や貴金属層を形成する際に生じる廃液を処理する必要がないため、環境負荷を低減できる。 In the present invention, since the fired layer contains at least one of platinum and palladium, it is possible to suppress the diffusion of the copper component of the base material into the fired layer. Further, since the fired layer contains at least one kind of gold or silver, when the copper terminal material is used as a connector, the contact resistance at the contact portion can be reduced and the contact reliability can be improved. Therefore, compared to the conventional configuration in which two layers of a base layer and a noble metal layer are formed on the surface of a base material made of copper or a copper alloy, it is as simple as forming one fired layer on a part of the surface of the base material. With the configuration, it is possible to suppress the diffusion of the copper component and improve the contact reliability. Further, since the film can be formed without using the plating method, it is not necessary to treat the waste liquid generated when the underlayer or the noble metal layer is formed by the plating method, so that the environmental load can be reduced.

本発明の銅端子材の好ましい態様としては、前記焼成層において金及び銀の少なくとも一種の成分比率が１０質量％以上７０質量％以下であり、白金及びパラジウムの少なくとも一種の成分比率が３０質量％以上９０質量％以下であり、かつ、各前記成分比率の和が９５質量％以上であるとよい。 As a preferred embodiment of the copper terminal material of the present invention, the component ratio of at least one of gold and silver is 10% by mass or more and 70% by mass or less in the fired layer, and the component ratio of at least one of platinum and palladium is 30% by mass. It is preferable that the content is 90% by mass or less and the sum of the component ratios is 95% by mass or more.

ここで、焼成層において金及び銀の少なくとも一種の成分比率が１０質量％未満である場合、接触抵抗が増加して上記接点信頼性が低下するおそれがある。一方、金又は銀の少なくとも一種の成分比率が７０質量％を超える場合、白金及びパラジウムの少なくとも一種の成分比率が３０質量％未満となるため、基材の銅成分の焼成層への拡散防止効果が低減する。また、白金及びパラジウムの少なくとも一種の成分比率が９０質量％を超える場合、焼成層内の空隙率が高くなり、焼成層の強度が低下する。さらに、金及び銀の少なくとも一種の成分比率及び白金及びパラジウムの少なくとも一種の成分比率の和が９５質量％未満であると、これら以外の成分が多くなるため、上記接点信頼性が低下し、かつ基材の銅成分の焼成層への拡散防止効果が低減する。
これに対し、上記態様では、焼成層において金及び銀の少なくとも一種の成分比率が１０質量％以上７０質量％以下であり、白金及びパラジウムの少なくとも一種の成分比率が３０質量％以上９０質量％以下であり、各成分比率の和が９５質量％以上であることから、焼成層への銅成分の拡散を確実に抑制し、かつ、接点信頼性をより高めることができる。 Here, when the component ratio of at least one of gold and silver is less than 10% by mass in the fired layer, the contact resistance may increase and the contact reliability may decrease. On the other hand, when the component ratio of at least one kind of gold or silver exceeds 70% by mass, the component ratio of at least one kind of platinum and palladium is less than 30% by mass, so that the effect of preventing the diffusion of the copper component of the base material into the fired layer is achieved. Is reduced. Further, when the component ratio of at least one of platinum and palladium exceeds 90% by mass, the porosity in the fired layer becomes high and the strength of the fired layer decreases. Further, when the sum of the component ratio of at least one of gold and silver and the component ratio of at least one of platinum and palladium is less than 95% by mass, the components other than these are increased, so that the contact reliability is lowered and the contact reliability is lowered. The effect of preventing the diffusion of the copper component of the base material into the fired layer is reduced.
On the other hand, in the above aspect, at least one component ratio of gold and silver is 10% by mass or more and 70% by mass or less, and at least one component ratio of platinum and palladium is 30% by mass or more and 90% by mass or less in the fired layer. Since the sum of the ratios of the respective components is 95% by mass or more, the diffusion of the copper component into the fired layer can be reliably suppressed and the contact reliability can be further improved.

本発明の銅端子材の好ましい態様としては、前記焼成層の空隙率が２０％以下であるとよい。
焼成層の空隙率が２０％を超えている場合、焼成層の強度が低下する。これに対し、上記態様では、焼成層の空隙率が２０％以下であるので、焼成層の強度を高めることができる。 As a preferred embodiment of the copper terminal material of the present invention, the porosity of the fired layer is preferably 20% or less.
When the porosity of the fired layer exceeds 20%, the strength of the fired layer decreases. On the other hand, in the above aspect, since the porosity of the fired layer is 20% or less, the strength of the fired layer can be increased.

本発明の銅端子材の好ましい態様としては、前記焼成層の膜厚は、０．３μｍ以上３．０μｍ以下であるとよい。
焼成層の膜厚が０．３μｍ以下であると、基材からのＣｕ成分の拡散を防止する効果が乏しくなることから上記接点信頼性が低下し、膜厚が３．０μｍを超えると焼結性が低下し焼成層の空隙率が上昇する。
これに対し、上記態様では、焼成層の膜厚が０．３μｍ以上３．０μｍ以下であるため、基材からのＣｕ成分の拡散を確実に抑制し、かつ、空隙率の上昇を抑制できるので、焼成層の接点信頼性を高めることができる。 As a preferred embodiment of the copper terminal material of the present invention, the film thickness of the fired layer is preferably 0.3 μm or more and 3.0 μm or less.
When the film thickness of the fired layer is 0.3 μm or less, the effect of preventing the diffusion of Cu components from the substrate is poor, so that the contact reliability is lowered, and when the film thickness exceeds 3.0 μm, sintering is performed. The property decreases and the porosity of the fired layer increases.
On the other hand, in the above aspect, since the film thickness of the fired layer is 0.3 μm or more and 3.0 μm or less, the diffusion of Cu components from the substrate can be reliably suppressed and the increase in porosity can be suppressed. , The contact reliability of the fired layer can be improved.

本発明の銅端子材の製造方法は、銅又は銅合金からなる基材の表面の一部に、金及び銀の少なくとも一種の粉末と、白金及びパラジウムの少なくとも一種の粉末と、を含む塗布材を塗布した後、塗布された前記塗布材にレーザ光を照射することにより前記塗布材を焼成して焼成層を形成しており、前記焼成層において金及び銀の少なくとも一種の成分比率が１０質量％以上７０質量％以下であり、白金及びパラジウムの少なくとも一種の成分比率が３０質量％以上９０質量％以下であり、かつ、各前記成分比率の和が９５質量％以上であり、前記焼成層の空隙率が２０％以下、前記焼成層の膜厚が０．３μｍ以上３．０μｍ以下である。
このような構成によれば、めっき法等を用いることなく銅成分の拡散を抑制し、かつ接点信頼性を高めることができる銅端子材を提供できる。
この場合、前記レーザ光は、固体レーザ、ファイバーレーザ、半導体レーザもしくはガスレーザであるとともに、波長が４００ｎｍ以上１１μｍ以下の範囲であり、前記塗布材表面における単位面積当たりの照射エネルギーが１．０×１０ ２ Ｊ／ｃｍ ２ 以上１．０×１０ ６ Ｊ／ｃｍ ２ 以下となるように照射されるとよい。 The method for producing a copper terminal material of the present invention is a coating material containing at least one powder of gold and silver and at least one powder of platinum and palladium on a part of the surface of a base material made of copper or a copper alloy. After coating, the coated material is fired by irradiating the coated material with a laser beam to form a fired layer , and the fired layer has a component ratio of at least one of gold and silver of 10 mass. % Or more and 70% by mass or less, the component ratio of at least one of platinum and palladium is 30% by mass or more and 90% by mass or less, and the sum of the component ratios is 95% by mass or more, and the fired layer. The void ratio is 20% or less, and the thickness of the fired layer is 0.3 μm or more and 3.0 μm or less .
According to such a configuration, it is possible to provide a copper terminal material capable of suppressing diffusion of a copper component and improving contact reliability without using a plating method or the like.
In this case, the laser beam is a solid-state laser, a fiber laser, a semiconductor laser or a gas laser, and has a wavelength in the range of 400 nm or more and 11 μm or less, and the irradiation energy per unit area on the surface of the coating material is 1.0 × 10. It is advisable to irradiate with 2 J / cm 2 or more and 1.0 × 10 6 J / cm 2 or less.

本発明によれば、銅端子材において、端子材の接点箇所に銅又は銅合金からなる基材の表面の一部に、金及び銀の少なくとも一種と、白金及びパラジウムの少なくとも一種とを含む焼成層を形成することで、接点信頼性を向上させ、かつ銅成分の拡散を抑制でき、また、この銅端子材の被膜形成において廃液等の処理を不要にできる。 According to the present invention, in a copper terminal material, firing containing at least one kind of gold and silver and at least one kind of platinum and palladium in a part of the surface of a base material made of copper or a copper alloy at a contact point of the terminal material. By forming the layer, the contact reliability can be improved and the diffusion of the copper component can be suppressed, and the treatment of waste liquid or the like can be eliminated in the film formation of the copper terminal material.

本発明の一実施形態に係る銅端子材を模式的に示す断面図である。It is sectional drawing which shows typically the copper terminal material which concerns on one Embodiment of this invention. 上記実施形態の銅端子材の製造方法を示すフローチャートである。It is a flowchart which shows the manufacturing method of the copper terminal material of the said embodiment. 上記銅端子材の製造途中においてペーストにレーザ光を照射している状態を模式的に示す断面図である。It is sectional drawing which shows typically the state that the paste is irradiated with the laser beam in the middle of manufacturing the copper terminal material.

以下、本発明の一実施形態について説明する。
＜銅端子材の構成＞
実施形態の銅端子材１は、図１に断面を模式的に示したように、銅または銅合金からなる基材２上に、焼成層３が積層されている。
基材２は、銅または銅合金からなるものであれば、特に、その組成が限定されるものではない。 Hereinafter, an embodiment of the present invention will be described.
<Composition of copper terminal material>
In the copper terminal material 1 of the embodiment, the fired layer 3 is laminated on the base material 2 made of copper or a copper alloy, as schematically shown in the cross section in FIG.
The composition of the base material 2 is not particularly limited as long as it is made of copper or a copper alloy.

焼成層３は、厚さが０．３μｍ以上３．０μｍ以下であり、金（Ａｕ）及び銀（Ａｇ）の少なくとも一種と、白金（Ｐｔ）及びパラジウム（Ｐｄ）の少なくとも一種とを含む貴金属層である。焼成層３は、金及び銀の少なくとも一種と、白金及びパラジウムの少なくとも一種とを含む金属層であるから、金及び白金からなる焼成層３、金及びパラジウムからなる焼成層３、銀及び白金からなる焼成層３、もしくは銀及びパラジウムからなる焼成層３の他、金、銀及び白金からなる焼成層３等、これらの３種以上を含む焼成層３としてもよい。
いずれの場合も、焼成層３全体としての厚さが０．３μｍ以上３．０μｍ以下である。この焼成層３は、基材２からの銅の拡散を防止する機能があり、その厚さが０．３μｍ未満では、銅の拡散を防止する効果が乏しく、厚さが３．０μｍを超えるとプレス加工時に割れが生じ易い。また、焼結層３の厚さが３．０μｍを超えると、焼結性が低下し、焼結層３の空隙率が上昇する。 The fired layer 3 has a thickness of 0.3 μm or more and 3.0 μm or less, and is a noble metal layer containing at least one of gold (Au) and silver (Ag) and at least one of platinum (Pt) and palladium (Pd). Is. Since the fired layer 3 is a metal layer containing at least one of gold and silver and at least one of platinum and palladium, the fired layer 3 is made of gold and platinum, the fired layer 3 is made of gold and palladium, and the fired layer 3 is made of silver and platinum. In addition to the fired layer 3 made of silver and palladium, the fired layer 3 made of gold, silver and platinum, and the like, the fired layer 3 containing three or more of these may be used.
In either case, the thickness of the fired layer 3 as a whole is 0.3 μm or more and 3.0 μm or less. The fired layer 3 has a function of preventing the diffusion of copper from the base material 2, and if the thickness is less than 0.3 μm, the effect of preventing the diffusion of copper is poor, and if the thickness exceeds 3.0 μm, the effect is poor. Cracks are likely to occur during press working. Further, when the thickness of the sintered layer 3 exceeds 3.0 μm, the sinterability is lowered and the porosity of the sintered layer 3 is increased.

また、焼成層３においては、金及び銀の少なくとも一種以上の成分比率が１０質量％以上７０質量％以下であり、白金及びパラジウムの少なくとも一種以上の成分比率が３０質量％以上９０質量％以下であり、かつ、各成分比率の和が９５質量％以上に設定されている。このため、焼成層３が金及び銀と、白金又はパラジウムとを含む場合には、金及び銀を合計したものの成分比率が１０質量％以上９０質量％以下となり、焼成層３が金又は銀と、白金及びパラジウムとを含む場合には、白金及びパラジウムを合計したものの成分比率が３０質量％以上９０質量％以下となる。
この焼成層３は、銅の拡散を防止する他、コネクタとして用いられる銅端子材１の接点信頼性を高める機能を有し、焼成層３において金及び銀の少なくとも一種の成分比率が１０質量％未満である場合、上記接点信頼性が低下する一方、金又は銀の少なくとも一種の成分比率が７０質量％を超える場合、白金及びパラジウムの少なくとも一種の成分比率が３０質量％未満となるため、基材２の銅成分の焼成層３への拡散を抑制できないからである。さらに、金及び銀の少なくとも一種の成分比率及び白金及びパラジウムの少なくとも一種の成分比率の和が９５質量％未満であると、上記接点信頼性及び基材２の銅成分の焼成層３への拡散を効果的に抑制できない。このため、焼結層３は、ルテニウム、オスミウム、ロジウム及びイリジウムの少なくともいずれかを成分比率５質量％未満の範囲で含んでいてもよい。
また、白金及びパラジウムの少なくとも一種の成分比率が９０質量％を超える場合、焼成層３内の空隙率が高くなり、焼成層３の強度が低下する。このため、焼成層３内の空隙率は、２０％以下に設定されている。 Further, in the fired layer 3, the component ratio of at least one kind of gold and silver is 10% by mass or more and 70% by mass or less, and the component ratio of at least one kind of platinum and palladium is 30% by mass or more and 90% by mass or less. Yes, and the sum of the ratios of each component is set to 95% by mass or more. Therefore, when the fired layer 3 contains gold and silver and platinum or palladium, the component ratio of the total of gold and silver is 10% by mass or more and 90% by mass or less, and the fired layer 3 is gold or silver. , Platinum and palladium, the total component ratio of platinum and palladium is 30% by mass or more and 90% by mass or less.
The fired layer 3 has a function of preventing the diffusion of copper and enhancing the contact reliability of the copper terminal material 1 used as a connector, and the component ratio of at least one of gold and silver in the fired layer 3 is 10% by mass. If it is less than, the contact reliability is lowered, while if the component ratio of at least one of gold or silver exceeds 70% by mass, the component ratio of at least one of platinum and palladium is less than 30% by mass. This is because the diffusion of the copper component of the material 2 into the fired layer 3 cannot be suppressed. Further, when the sum of the component ratio of at least one of gold and silver and the component ratio of at least one of platinum and palladium is less than 95% by mass, the contact reliability and the diffusion of the copper component of the base material 2 into the fired layer 3 Cannot be effectively suppressed. Therefore, the sintered layer 3 may contain at least one of ruthenium, osmium, rhodium, and iridium in a component ratio of less than 5% by mass.
Further, when the component ratio of at least one of platinum and palladium exceeds 90% by mass, the porosity in the fired layer 3 becomes high, and the strength of the fired layer 3 decreases. Therefore, the porosity in the fired layer 3 is set to 20% or less.

例えば、焼成層３が白金合金（Ａｕ－Ｐｔ合金又はＡｇ－Ｐｔ合金）からなる場合には、その組成は、Ａｕ－（３０質量％～９０質量％）Ｐｔ、又はＡｇ－（５０質量％～９０質量％）Ｐｔであることが好ましい。また、焼成層３がパラジウム合金（Ａｕ－Ｐｄ合金又はＡｇ－Ｐｄ合金）からなる場合には、その組成は、Ａｕ－（３５質量％～９０質量％）Ｐｄ、又はＡｇ－（７５質量％～９０質量％）Ｐｔであることが好ましい。これらの成分比率にすることにより、基材２からの焼成層３への銅の拡散を抑制し、かつ、接点信頼性を高めることができる。 For example, when the fired layer 3 is made of a platinum alloy (Au-Pt alloy or Ag-Pt alloy), the composition thereof is Au- (30% by mass to 90% by mass) Pt or Ag- (50% by mass to). 90% by mass) Pt is preferable. When the fired layer 3 is made of a palladium alloy (Au-Pd alloy or Ag-Pd alloy), the composition thereof is Au- (35% by mass to 90% by mass) Pd or Ag- (75% by mass or more). 90% by mass) Pt is preferable. By setting these component ratios, it is possible to suppress the diffusion of copper from the base material 2 to the fired layer 3 and to improve the contact reliability.

次に、この銅端子材１の製造方法について説明する。
まず、基材２として、銅または銅合金からなる板材を用意し、図２に示す工程順で銅端子材１を製造する。
まず、この板材に脱脂、酸洗等をすることによって表面を清浄にする前処理を行う（前処理工程）。
次に、焼結層３のための塗布材として、例えば、金属粉末にバインダーもしくはレオロジー調整材を混合したペースト３´を塗布する（ペースト塗布工程）。このペースト３´に含まれる金属粉末は、例えば、金及び銀の少なくとも一種の粉末と、白金及びパラジウムの少なくとも一種の粉末とが混合されたものであり、この金属粉末の成分比率は、金及び銀の少なくとも一種の成分比率が１０質量％以上７０質量％以下であり、白金及びパラジウムの少なくとも一種の成分比率が３０質量％以上９０質量％以下である。また、バインダーとしては、４００℃以下での熱分解性が良好な高分子材料であることが好ましく、例えば、アクリル樹脂、ウレタン樹脂やポリアクリル酸、ポリビニルピロリドン、ポリエチレンイミン等を用いることが好適である。また、レオロジー調整剤としては、溶剤中で自己会合し、少量で溶剤の粘度を増加させることが可能な材料であることが好ましく、例えば、１２－ヒドロキシステアリン酸、硬化ひまし油、ベンジリデンソルビトール及びその誘導体、ラウロイル－L－グルタミン酸－α、γ－ジブチルアミド等を用いることが好適である。このような成分比率の金属粉末を含むペースト３´の粘度は、１Ｐａ・ｓ以上１００Ｐａ・ｓ以下であり、このペースト３´の塗布は、例えば、ディスペンサにより実行される。
なお、本実施形態では、上記金属粉末を含むペースト３´をディスペンサにより塗布することとしたが、例えば、上記金属粉末を含む粘度が１ｍＰａ・ｓ以上１０００ｍＰａ・ｓ未満のインクをインクジェット方式のプリンタ等により塗布してもよい。この際、インクは、上記金属粉末に水、エタノール、イソプロピルアルコール等のアルコール系溶剤、トルエン、ドデカン、ｎ－デカン、テトラデカン、ＡＦ－ソルベント等の炭化水素系溶剤等の溶剤を単独もしくは混合したものが用いられる。また、上記金属粉末は、例えば白金合金又はパラジウム合金等の合金粉末であってもよく、その成分比率が上記範囲内であればよい。 Next, a method for manufacturing the copper terminal material 1 will be described.
First, a plate material made of copper or a copper alloy is prepared as the base material 2, and the copper terminal material 1 is manufactured in the order of the steps shown in FIG.
First, a pretreatment for cleaning the surface is performed by degreasing, pickling, etc. on this plate material (pretreatment step).
Next, as a coating material for the sintered layer 3, for example, a paste 3'in which a binder or a rheology adjusting material is mixed with a metal powder is applied (paste coating step). The metal powder contained in this paste 3'is, for example, a mixture of at least one powder of gold and silver and at least one powder of platinum and palladium, and the component ratio of this metal powder is gold and. The component ratio of at least one kind of silver is 10% by mass or more and 70% by mass or less, and the component ratio of at least one kind of platinum and palladium is 30% by mass or more and 90% by mass or less. Further, the binder is preferably a polymer material having good thermal decomposability at 400 ° C. or lower, and for example, acrylic resin, urethane resin, polyacrylic acid, polyvinylpyrrolidone, polyethyleneimine and the like are preferably used. be. The rheology adjuster is preferably a material that self-associates in the solvent and can increase the viscosity of the solvent in a small amount. For example, 12-hydroxystearic acid, hardened castor oil, benzylidene sorbitol and its derivatives thereof. , Lauroyl-L-glutamic acid-α, γ-dibutylamide and the like are preferably used. The viscosity of the paste 3'containing the metal powder having such a component ratio is 1 Pa · s or more and 100 Pa · s or less, and the application of the paste 3'is carried out by, for example, a dispenser.
In the present embodiment, the paste 3'containing the metal powder is applied by a dispenser. For example, an ink jet printer or the like using an ink containing the metal powder and having a viscosity of 1 mPa · s or more and less than 1000 mPa · s can be applied. May be applied. At this time, the ink is a mixture of the above metal powder with an alcohol solvent such as water, ethanol or isopropyl alcohol, or a solvent such as a hydrocarbon solvent such as toluene, dodecane, n-decane, tetradecane or AF-solvent. Is used. Further, the metal powder may be an alloy powder such as a platinum alloy or a palladium alloy, and the component ratio thereof may be within the above range.

このようにして基材２の上にペースト３´を塗布し、乾燥させた後、図３に示すように、そのペースト３´の表面にレーザ光Ｌを所定時間（例えば、０．０１～１秒間）照射して、ペースト３´を加熱する。このレーザ光Ｌは、照射面内（ペースト３´の表面内）に均一なレーザ光であり、このレーザ光Ｌの焦点サイズは０．５～５ｍｍ角に設定されている。この焼成層３が形成される部分のサイズが、レーザ光Ｌの焦点サイズよりも小さい場合は、レーザ光Ｌを走査（スキャン）することなく照射する。それに対して、焼成層３が形成される部分のサイズが、レーザ光Ｌの焦点サイズよりも大きい場合は、ガルバノミラー等のスキャニングミラーを使用し、焼成層３が形成される部分全体に、レーザ光Ｌを走査（スキャン）して照射する（レーザ光照射工程）。
レーザ光としては、固体レーザ、ファイバーレーザ、半導体レーザ（ＬＤ）もしくはガスレーザを用いることができる。レーザ光の波長は、４００ｎｍ以上１１μｍ以下の範囲であり、ペースト３´表面における単位面積当たりの照射エネルギーが１．０×１０２Ｊ／ｃｍ２以上１．０×１０６Ｊ／ｃｍ２以下となるように照射する。 After the paste 3'is applied onto the base material 2 in this way and dried, the laser beam L is applied to the surface of the paste 3'for a predetermined time (for example, 0.01 to 1) as shown in FIG. Irradiate (for seconds) to heat the paste 3'. The laser beam L is a uniform laser beam in the irradiation surface (inside the surface of the paste 3'), and the focal size of the laser beam L is set to 0.5 to 5 mm square. When the size of the portion where the fired layer 3 is formed is smaller than the focal size of the laser beam L, the laser beam L is irradiated without being scanned. On the other hand, when the size of the portion where the firing layer 3 is formed is larger than the focal size of the laser beam L, a scanning mirror such as a galvano mirror is used, and the laser is applied to the entire portion where the firing layer 3 is formed. The light L is scanned and irradiated (laser light irradiation step).
As the laser beam, a solid-state laser, a fiber laser, a semiconductor laser (LD) or a gas laser can be used. The wavelength of the laser beam is in the range of 400 nm or more and 11 μm or less, and the irradiation energy per unit area on the surface of the paste 3'is 1.0 × 10 2 J / cm 2 or more and 1.0 × 10 6 J / cm 2 or less. Irradiate so that it becomes.

レーザ光は波長の揃った高エネルギー密度の光を局所的に集光することが可能という特徴を有していることから、レーザ光を使用することにより、複雑な工程を必要とすることなく、短時間に、ペースト３´を焼成させ、焼成層３を形成することができる。
このようにして、ペースト３´にレーザ光照射工程を施すことにより、金及び銀の少なくとも一種以上の成分比率が１０質量％以上７０質量％以下であり、白金及びパラジウムの少なくとも一種以上の成分比率が３０質量％以上９０質量％以下であり、各成分比率の和が９５質量％以上の焼成層３が形成される。 Since laser light has the characteristic of being able to locally focus light with high energy density with the same wavelength, the use of laser light eliminates the need for complicated processes. The paste 3'can be fired in a short time to form the fired layer 3.
By subjecting the paste 3'to a laser beam irradiation step in this way, the component ratio of at least one kind of gold and silver is 10% by mass or more and 70% by mass or less, and the component ratio of at least one kind of platinum and palladium. Is 30% by mass or more and 90% by mass or less, and the fired layer 3 having a sum of each component ratio of 95% by mass or more is formed.

このようにして基材２の表面の一部に焼成層３が形成された銅端子材１に対してプレス加工等を施し、接点として用いられる部分に焼成層３が配置される端子を形成する。
この端子は、焼成層３が積層されている部分では、上記成分比率の白金及びパラジウムの少なくとも一種を含んでいるため、基材２からの銅の焼成層３への拡散を有効に防止することができ、優れた耐熱性を維持することができる。例えば、２００℃の温度に長時間（～１０００時間）晒しても、基材２の銅が焼成層３に拡散することを抑制できる。
また、焼成層３は、上記成分比率の金又は銀の少なくとも一種を含んでいるので、接点箇所の接触抵抗を低減させることができ、接点信頼性を高めることができる。したがって、銅又は銅合金からなる基材２の表面に下地層及び貴金属層の２層を形成する従来の構成に比べて、基材２の表面の一部に焼成層３を１層形成するだけの簡単な構成で、銅成分の拡散を抑制し、かつ接点信頼性を高めることができる。また、めっき法を用いることなく貴金属を含む被膜を形成できることから、めっき法を用いて下地層や貴金属層を形成する際に生じる廃液を処理する必要がないため、環境負荷を低減できる。 In this way, the copper terminal material 1 having the fired layer 3 formed on a part of the surface of the base material 2 is press-processed to form a terminal on which the fired layer 3 is arranged at a portion used as a contact. ..
Since this terminal contains at least one of platinum and palladium having the above-mentioned component ratios in the portion where the fired layer 3 is laminated, it is necessary to effectively prevent the diffusion of copper from the base material 2 to the fired layer 3. And can maintain excellent heat resistance. For example, even if it is exposed to a temperature of 200 ° C. for a long time (up to 1000 hours), it is possible to prevent the copper of the base material 2 from diffusing into the fired layer 3.
Further, since the fired layer 3 contains at least one kind of gold or silver having the above-mentioned component ratio, the contact resistance at the contact portion can be reduced and the contact reliability can be improved. Therefore, as compared with the conventional configuration in which two layers of the base layer and the noble metal layer are formed on the surface of the base material 2 made of copper or a copper alloy, only one layer of the fired layer 3 is formed on a part of the surface of the base material 2. With this simple configuration, it is possible to suppress the diffusion of copper components and improve contact reliability. Further, since the film containing the noble metal can be formed without using the plating method, it is not necessary to treat the waste liquid generated when the underlayer or the noble metal layer is formed by the plating method, so that the environmental load can be reduced.

その他、細部構成は実施形態の構成のものに限定されるものではなく、本発明の趣旨を逸脱しない範囲において種々の変更を加えることが可能である。 In addition, the detailed configuration is not limited to the configuration of the embodiment, and various changes can be made without departing from the spirit of the present invention.

基材として、表１に示すＣＤＡ（Ｃｏｐｐｅｒ Ｄｅｖｅｌｏｐｍｅｎｔ Ａｓｓｏｃｉａｔｉｏｎ）合金番号の厚さ０．２５ｍｍの材料を使用した。前処理として、電解脱脂（ＮａＯＨ水溶液６０ｇ／リットルを用いて、液温６０℃、電流密度２．５ＡＳＤ（Ａ／ｄｍ２）、脱脂時間６０秒間）及び酸洗（硫酸１０％水溶液、液温２５℃、浸漬時間３０秒間）を行った。 As the base material, a material having a thickness of 0.25 mm having a CDA (Copper Development Association) alloy number shown in Table 1 was used. As pretreatment, electrolytic degreasing (using 60 g / liter of NaOH aqueous solution, liquid temperature 60 ° C., current density 2.5 ASD (A / dm2), degreasing time 60 seconds) and pickling (10% aqueous sulfuric acid solution, liquid temperature 25 ° C.) , Immersion time 30 seconds).

また、焼成層は、基材上にペーストを塗布し、このペーストにレーザ光を照射することにより形成した。このペーストに含まれる貴金属の成分比率及び膜厚は、表１に示す通りである。
レーザ光の照射は、焼結層が形成される箇所の所定のエリアに対して、レーザ光の波長が１０７０ｎｍ、ペースト表面における単位面積当たりの照射エネルギーが１．５×１０３Ｊ／ｃｍ２となるように照射を行った。尚、焦点サイズよりも焼成層が形成されるエリアが大きい場合は、上記レーザ光をスキャンすることによりエリア全体に照射した。 Further, the fired layer was formed by applying a paste on a substrate and irradiating the paste with a laser beam. The composition ratio and film thickness of the noble metal contained in this paste are as shown in Table 1.
In the irradiation of the laser light, the wavelength of the laser light is 1070 nm and the irradiation energy per unit area on the paste surface is 1.5 × 10 3 J / cm 2 with respect to the predetermined area where the sintered layer is formed. Irradiation was performed so as to be. When the area where the fired layer was formed was larger than the focal size, the entire area was irradiated by scanning the laser beam.

（焼結層の空隙率）
焼成層の空隙率は、焼成層が形成された端子材の断面をクロスセクションポリッシャ加工により断面を研磨したサンプルを、電子顕微鏡（ＳＥＭ）を用いて、倍率が５０００倍での観察により得られた画像より、焼成層中の空隙の総面積を、空隙を含む焼成層の面積で除した値の百分率を空隙率とした。 (Porosity of sintered layer)
The porosity of the fired layer was obtained by observing a sample obtained by polishing the cross section of the terminal material on which the fired layer was formed by cross-section polisher processing using an electron microscope (SEM) at a magnification of 5000 times. From the image, the porosity was defined as the percentage of the value obtained by dividing the total area of the voids in the fired layer by the area of the fired layer including the voids.

（膜厚及び膜厚バラつき）
焼成層の膜厚及び膜厚バラつきは、焼成層が形成された端子材の断面をクロスセクションポリッシャ加工により断面を研磨したサンプルを、電子顕微鏡（ＳＥＭ）を用いて、倍率が５００倍での観察により得られた画像より、焼成層の膜厚を任意に５か所測定し、５か所の膜厚の平均値を膜厚とし、標準偏差の値を膜厚バラつきとした。 (Film thickness and film thickness variation)
For the film thickness and film thickness variation of the fired layer, observe the sample obtained by polishing the cross section of the terminal material on which the fired layer is formed by cross-section polisher processing at a magnification of 500 times using an electron microscope (SEM). The film thickness of the fired layer was arbitrarily measured at 5 points, the average value of the film thicknesses at the 5 points was taken as the film thickness, and the standard deviation value was taken as the film thickness variation.

（初期抵抗及び接触抵抗変化率の評価方法）
最表面の焼成層の接触抵抗は、ＪＣＢＡ－Ｔ３２３に準拠し、４端子接触抵抗試験機を用いて、摺動式（１ｍｍ）で荷重０．９８Ｎ時の接触抵抗を測定した。まず、焼成層形成直後の初期の接触抵抗を測定した後、熱処理として、恒温槽を用いて、大気雰囲気中、２００℃、１０００時間保持後、再度接触抵抗を測定した。
初期抵抗値については、５ｍΩ未満のものを「〇」とし、５ｍΩ以上１０ｍΩ以下のものを「△」とし、１０ｍΩより大きいものを「×」とした。
また、接触抵抗変化率については、初期の測定から２００℃、１０００時間保持後の測定値の変化率が、１０％未満のものを「◎」とし、１０％以上、２０％未満のものを「○」とし、２０％以上、２５％未満のものを「△」とし、２５％以上のものを「×」とした。
これらの結果を表１に示す。 (Evaluation method of initial resistance and contact resistance change rate)
The contact resistance of the fired layer on the outermost surface was measured in accordance with JCBA-T323 using a 4-terminal contact resistance tester in a sliding manner (1 mm) at a load of 0.98 N. First, the initial contact resistance immediately after the formation of the fired layer was measured, and then the contact resistance was measured again after holding at 200 ° C. for 1000 hours in an air atmosphere using a constant temperature bath as a heat treatment.
Regarding the initial resistance value, those with less than 5 mΩ were designated as “◯”, those with 5 mΩ or more and 10 mΩ or less were designated as “Δ”, and those larger than 10 mΩ were designated as “×”.
Regarding the contact resistance change rate, those with a change rate of less than 10% in the measured value after holding at 200 ° C for 1000 hours from the initial measurement are marked with "◎", and those with 10% or more and less than 20% are marked with "◎". ◯ ”, those with 20% or more and less than 25% were marked with“ Δ ”, and those with 25% or more were marked with“ × ”.
These results are shown in Table 1.

Figure 0007024358000001
Figure 0007024358000001

表１の結果からわかるように、銅又は銅合金からなる基材の表面の一部に、金及び銀の少なくとも一種と、白金及びパラジウムの少なくとも一種とを含む焼成層は、初期抵抗値が全て「△」以上であり、初期抵抗値における接点信頼性が高いことがわかった。特に、基材上に形成される焼成層において金及び銀の少なくとも一種の成分比率が１０質量％以上７０質量％以下であり、白金及びパラジウムの少なくとも一種の成分比率が３０質量％以上９０質量％以下であり、空隙率が２０％以下であり、かつ、焼成層の膜厚が０．３μｍ以上３．０μｍ以下であるのものは、初期抵抗値及び接触抵抗変化率のいずれもが「〇」以上であり、特に接点信頼性が高かった。 As can be seen from the results in Table 1, the fired layer containing at least one of gold and silver and at least one of platinum and palladium on a part of the surface of the base material made of copper or a copper alloy has all the initial resistance values. It was found to be "Δ" or higher, and the contact reliability at the initial resistance value was high. In particular, in the fired layer formed on the substrate, the component ratio of at least one of gold and silver is 10% by mass or more and 70% by mass or less, and the component ratio of at least one of platinum and palladium is 30% by mass or more and 90% by mass. If the porosity is 20% or less and the thickness of the fired layer is 0.3 μm or more and 3.0 μm or less, both the initial resistance value and the contact resistance change rate are “〇”. As mentioned above, the contact reliability was particularly high.

１ 銅端子材
２ 基材
３ 焼成層
３´ ペースト（塗布材）
Ｌ レーザ光 1 Copper terminal material 2 Base material 3 Firing layer 3'Paste (coating material)
L laser light

Claims (2)

銅又は銅合金からなる基材の表面の一部に、金及び銀の少なくとも一種の粉末と、白金及びパラジウムの少なくとも一種の粉末と、を含む塗布材を塗布した後、塗布された前記塗布材にレーザ光を照射することにより前記塗布材を焼成して焼成層を形成しており、
前記焼成層において金及び銀の少なくとも一種の成分比率が１０質量％以上７０質量％以下であり、白金及びパラジウムの少なくとも一種の成分比率が３０質量％以上９０質量％以下であり、かつ、各前記成分比率の和が９５質量％以上であり、前記焼成層の空隙率が２０％以下、前記焼成層の膜厚が０．３μｍ以上３．０μｍ以下であることを特徴とする銅端子材の製造方法。 A coating material containing at least one powder of gold and silver and at least one powder of platinum and palladium is applied to a part of the surface of a base material made of copper or a copper alloy, and then the coating material is applied. By irradiating the coating material with a laser beam, the coating material is fired to form a fired layer.
In the fired layer, the component ratio of at least one of gold and silver is 10% by mass or more and 70% by mass or less, the component ratio of at least one of platinum and palladium is 30% by mass or more and 90% by mass or less, and each of the above. Manufacture of a copper terminal material characterized in that the sum of the component ratios is 95% by mass or more, the porosity of the fired layer is 20% or less, and the film thickness of the fired layer is 0.3 μm or more and 3.0 μm or less. Method. 前記レーザ光は、固体レーザ、ファイバーレーザ、半導体レーザもしくはガスレーザであるとともに、波長が４００ｎｍ以上１１μｍ以下の範囲であり、前記塗布材表面における単位面積当たりの照射エネルギーが１．０×１０２Ｊ／ｃｍ２以上１．０×１０６Ｊ／ｃｍ２以下となるように照射されることを特徴とする請求項１に記載の銅端子材の製造方法。 The laser beam is a solid-state laser, a fiber laser, a semiconductor laser or a gas laser, has a wavelength in the range of 400 nm or more and 11 μm or less, and has an irradiation energy of 1.0 × 10 2 J / per unit area on the surface of the coating material. The method for manufacturing a copper terminal material according to claim 1 , wherein the irradiation is performed so as to be cm 2 or more and 1.0 × 10 6 J / cm 2 or less.
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