JP2019099848A - Copper terminal material and production method of the same - Google Patents

Copper terminal material and production method of the same Download PDF

Info

Publication number
JP2019099848A
JP2019099848A JP2017229793A JP2017229793A JP2019099848A JP 2019099848 A JP2019099848 A JP 2019099848A JP 2017229793 A JP2017229793 A JP 2017229793A JP 2017229793 A JP2017229793 A JP 2017229793A JP 2019099848 A JP2019099848 A JP 2019099848A
Authority
JP
Japan
Prior art keywords
copper
mass
layer
platinum
terminal material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2017229793A
Other languages
Japanese (ja)
Other versions
JP7024358B2 (en
Inventor
隆二 植杉
Ryuji Uesugi
隆二 植杉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Materials Corp
Original Assignee
Mitsubishi Materials Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Materials Corp filed Critical Mitsubishi Materials Corp
Priority to JP2017229793A priority Critical patent/JP7024358B2/en
Publication of JP2019099848A publication Critical patent/JP2019099848A/en
Application granted granted Critical
Publication of JP7024358B2 publication Critical patent/JP7024358B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Powder Metallurgy (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Manufacturing Of Electrical Connectors (AREA)

Abstract

To provide a copper terminal material and a production method of the same which eliminates processing of drainage etc. in a terminal material composed of copper or copper alloy.SOLUTION: In the copper terminal material 1 of the invention, a burned layer 3 including at least one kind of gold and silver, and at least one kind of platinum and palladium in a part of a surface of a substrate 2 composed of copper or copper alloy, is formed. In the burned layer 3, a component ratio of at least one kind of gold and silver is 10 mass% or more and 70 mass% or less, a component ratio of at least one kind of platinum and palladium is 30 mass% or more and 90 mass% or less, and a sum of each component ratios is 95 mass% or more.SELECTED DRAWING: Figure 1

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及びその製造方法に関する。   The present invention relates to a copper terminal material provided with a coating containing a noble metal such as platinum or palladium, which is useful as a terminal for a connector used to connect an electrical wiring of an automobile or a consumer device, and a method of manufacturing the same.

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。
DESCRIPTION OF RELATED ART Conventionally, the terminal for connectors used for the connection of electrical wiring, such as a motor vehicle and a household appliance, is known. As a terminal material used as such a connector terminal, a plating layer composed of a metal such as nickel or cobalt is formed on the surface of a copper or copper alloy substrate as a base layer, and tin or the like is formed on the upper surface of the base layer. The terminal material in which the metal plating layer was formed is disclosed (for example, refer to patent documents 1).
In the terminal material described in Patent Document 1, since the plating layer of nickel, cobalt or the like is formed on the surface of the copper or copper alloy substrate, the copper or copper alloy is formed on the metal plating layer of tin or the like located on the surface. Diffusion of the copper component of the base material is suppressed.

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)。   Moreover, in order to improve the reliability of the contact point of the terminal material, a method of partially plating a noble metal such as gold or silver on the contact point has been proposed (see, for example, Patent Document 2).

特開平8−7960号公報JP-A-8-7960 特開2000−87289号公報JP, 2000-87289, A

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 the underlayer such as nickel or cobalt is formed, the process is complicated. Since this base layer is formed using a plating method, it is necessary to treat the plating waste solution and to take measures to reduce the environmental load. In addition, in the partial plating method described in Patent Document 2, when partially plating noble metals such as gold and silver on contact points, processes and apparatuses such as masking become complicated, and use of poisons such as cyanide and treatment of waste liquid Measures are needed to reduce environmental load.

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及びそ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 it is an object of the present invention to provide a copper terminal material which does not require treatment with waste liquid or the like in forming a film of a terminal material made of copper or copper alloy. Do.

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 part of the surface of a substrate made of copper or 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, diffusion of the copper component of the substrate to the fired layer can be suppressed. Further, since the fired layer contains at least one of gold and 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, 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 made of copper or copper alloy, it is simple to form one fired layer on a part of the surface of the base material. By the configuration, the diffusion of the copper component can be suppressed and the contact reliability can be enhanced. In addition, since the film can be formed without using the plating method, it is not necessary to treat the waste solution generated when forming the underlayer or the noble metal layer by using 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。   In a preferred embodiment of the copper terminal material according to the present invention, at least one component ratio of gold and silver in the fired layer is 10% by mass to 70% by mass, and at least one component ratio of platinum and palladium is 30% by mass It is good that it is 90 mass% or less, and the sum of each said component ratio is 95 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 in the fired layer is less than 10% by mass, the contact resistance may be increased, and the contact reliability may be lowered. On the other hand, when 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, so the diffusion preventing effect of the copper component of the substrate to the fired layer Is reduced. Moreover, 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. Furthermore, if 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, components other than these increase, and the contact reliability decreases, and The effect of preventing the diffusion of the copper component of the base material to the fired layer is reduced.
On the other hand, in the above aspect, the component ratio of at least one of gold and silver in the fired layer is 10% by mass to 70% by mass, and the component ratio of at least one of platinum and palladium is 30% by mass to 90% by mass Since the sum of the component ratios is 95% by mass or more, the diffusion of the copper component to the fired layer can be reliably suppressed, and the contact reliability can be further enhanced.

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 preferable aspect of the copper terminal material of this invention, it is good for the porosity of the said baking layer to be 20% or less.
When the porosity of the fired layer exceeds 20%, the strength of the fired layer is reduced. 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 preferable aspect 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 the Cu component from the base material is poor, and the contact reliability is lowered. When the film thickness exceeds 3.0 μm, sintering occurs. The porosity 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 the Cu component from the base material can be reliably suppressed and the increase in porosity can be suppressed. And the contact reliability of the fired layer can be enhanced.

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を焼成して焼成層を形成する。
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。
The method for producing a copper terminal material according to the present invention is a coating material comprising a powder of at least one of gold and silver and at least one powder of platinum and palladium on a part of the surface of a substrate made of copper or copper alloy. Is applied, and then the applied material is fired to form a fired layer.
According to such a configuration, it is possible to provide a copper terminal material capable of suppressing the diffusion of the copper component and improving the contact reliability without using a plating method or the like.

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 the copper terminal material, firing is carried out including at least one kind of gold and silver and at least one kind of platinum and palladium in a part of the surface of the base made of copper or copper alloy at contact points of the terminal material. By forming the layer, it is possible to improve the contact reliability and to suppress the diffusion of the copper component, and it is possible to make unnecessary the treatment of waste liquid etc. 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 a sectional view showing typically the copper terminal material concerning one embodiment of the present 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 which is irradiating a laser beam to paste in the middle of manufacture of the said 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, as the cross section is schematically shown in FIG. 1, the fired layer 3 is laminated on the base material 2 made of copper or copper alloy.
The composition of the substrate 2 is not particularly limited as long as the substrate 2 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 to 3.0 μm, and is a noble metal layer including at least one of gold (Au) and silver (Ag), and at least one of platinum (Pt) and palladium (Pd). It 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 made of gold and platinum, the fired layer 3 made of gold and palladium, silver and platinum In addition to the fired layer 3 or the fired layer 3 formed of silver and palladium, the fired layer 3 such as gold, silver and platinum, or the like may be used as the fired layer 3 including three or more of these.
In any case, the thickness of the entire baked layer 3 is 0.3 μm or more and 3.0 μm or less. The baked layer 3 has a function of preventing the diffusion of copper from the base material 2. If the thickness is less than 0.3 μm, the effect of preventing the diffusion of copper is scarce, and if the thickness exceeds 3.0 μm Cracking is likely to occur during press working. When the thickness of the sintered layer 3 exceeds 3.0 μm, the sinterability decreases and the porosity of the sintered layer 3 increases.

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。
In the fired layer 3, the component ratio of at least one or more of gold and silver is 10% by mass to 70% by mass, and the component ratio of at least one or more of platinum and palladium is 30% by mass to 90% by mass And the sum of the ratio of each component is set to 95 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 to 90% by mass, and the fired layer 3 is formed of gold or silver When platinum and palladium are contained, the component ratio of the total of platinum and palladium is 30% by mass or more and 90% by mass or less.
The baked layer 3 has the function of preventing the diffusion of copper and enhancing the contact reliability of the copper terminal material 1 used as a connector, and in the baked layer 3, the proportion of at least one of gold and silver is 10% by mass. When it is less than the above, the contact reliability is lowered, while when at least one component ratio of gold or silver exceeds 70% by mass, at least one component ratio of platinum and palladium becomes less than 30% by mass. This is because the diffusion of the copper component of the material 2 into the sintered layer 3 can not be suppressed. Furthermore, 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 2 into the fired layer 3 Can not be effectively suppressed. Therefore, the sintered layer 3 may contain at least one of ruthenium, osmium, rhodium and iridium in a range of less than 5% by mass.
Moreover, when the component ratio of at least one of platinum and palladium exceeds 90% by mass, the porosity in the fired layer 3 is increased, and the strength of the fired layer 3 is reduced. For this reason, the porosity in the sintered 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 mass% to 90 mass%) Pt, or Ag- (50 mass% to It is preferable that it is 90 mass%) Pt. Moreover, when the baked layer 3 consists of palladium alloys (Au-Pd alloy or Ag-Pd alloy), the composition is Au- (35 mass%-90 mass%) Pd, or Ag- (75 mass%- It is preferable that it is 90 mass%) Pt. By using these component ratios, the diffusion of copper from the base material 2 to the sintered layer 3 can be suppressed, and the contact reliability can be enhanced.

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, the manufacturing method of this copper terminal material 1 is explained.
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 steps shown in FIG.
First, pretreatment is performed to clean the surface of the plate material by degreasing, pickling or the like (pretreatment step).
Next, as a coating material for the sintered layer 3, for example, a paste 3 'in which a binder or a rheology modifier is mixed with metal powder is applied (paste application 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 silver is 10% by mass to 70% by mass, and the component ratio of at least one platinum and palladium is 30% by mass to 90% by mass. The binder is preferably a polymer material having good thermal decomposability at 400 ° C. or less, and, for example, acrylic resin, urethane resin, polyacrylic acid, polyvinyl pyrrolidone, polyethylene imine, etc. are preferably used. is there. The rheology modifier is preferably a material capable of self-association in a solvent and increasing the viscosity of the solvent by a small amount, for example, 12-hydroxystearic acid, hydrogenated castor oil, benzylidene sorbitol and derivatives thereof It is preferable to use lauroyl-L-glutamic acid-α, γ-dibutylamide and the like. The viscosity of the paste 3 'containing the metal powder of such a component ratio is 1 Pa · s or more and 100 Pa · s or less, and the application of the paste 3' is performed by, for example, a dispenser.
In the present embodiment, although the paste 3 'containing the metal powder is applied by a dispenser, for example, an ink jet printer including an ink having a viscosity of 1 mPa · s or more and less than 1000 mPa · s is included. May be applied. At this time, the ink may be 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. The metal powder may be, for example, an alloy powder such as a platinum alloy or a palladium alloy, and the component ratio thereof may be in 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1.0×10J/cm以上1.0×10J/cm以下となるように照射する。
Thus, after applying paste 3 'on the base material 2 and drying it, as shown in FIG. 3, the laser beam L is applied to the surface of the paste 3' for a predetermined time (for example, 0.01 to 1) Irradiate and heat the paste 3 '. The laser beam L is a laser beam which is uniform in the irradiation plane (in 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 baked 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 fired layer 3 is formed is larger than the focal point size of the laser light L, a scanning mirror such as a galvano mirror is used, and the laser is used for the entire portion where the fired layer 3 is formed. The light L is scanned (scanned) and irradiated (laser light irradiation step).
As the laser beam, a solid 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 to 11 μm, and the irradiation energy per unit area on the surface of the paste 3 'is 1.0 × 10 2 J / cm 2 to 1.0 × 10 6 J / cm 2. Irradiate to become

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 feature of being able to locally collect light of high energy density with uniform 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.
Thus, by subjecting the paste 3 'to the laser beam irradiation step, the component ratio of at least one or more of gold and silver is 10% by mass to 70% by mass, and the component ratio of at least one or more 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 component ratios 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。
Thus, the copper terminal material 1 in which the sintered layer 3 is formed on a part of the surface of the base material 2 is subjected to pressing or the like to form a terminal in which the sintered layer 3 is disposed in a portion used as a contact. .
Since the terminal includes at least one of platinum and palladium in the component ratio in the portion where the fired layer 3 is laminated, the diffusion of copper from the substrate 2 to the fired layer 3 is effectively prevented. Can maintain excellent heat resistance. For example, even if it expose | bleached to the temperature of 200 degreeC for a long time (1000 hours), it can suppress that the copper of the base material 2 spread | diffuses in the baked layer 3. As shown in FIG.
In addition, since the fired layer 3 contains at least one of gold and silver having the component ratio described above, the contact resistance at the contact point can be reduced, and the contact reliability can be enhanced. Therefore, compared to the conventional configuration in which two layers of the base layer and the noble metal layer are formed on the surface of base material 2 made of copper or copper alloy, only one layer of baked layer 3 is formed on part of the surface of base material 2 With this simple configuration, the diffusion of the copper component can be suppressed and the contact reliability can be enhanced. In addition, since a film containing a noble metal can be formed without using a plating method, it is not necessary to treat the waste liquid generated when forming an underlayer or a noble metal layer using a 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 modifications can be made without departing from the scope 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 a substrate, a material with a thickness of 0.25 mm of a CDA (Copper Development Association) alloy number shown in Table 1 was used. As pretreatment, electrolytic degreasing (using NaOH aqueous solution 60 g / l, liquid temperature 60 ° C., current density 2.5 ASD (A / dm 2), 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1.5×10J/cm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。
In addition, the fired layer was formed by applying a paste on a substrate and irradiating the paste with a laser beam. The component ratio and the film thickness of the noble metal contained in this paste are as shown in Table 1.
The irradiation of the laser light is such that 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. It irradiated so that it might become. When the area where the fired layer is formed is larger than the focal point size, the entire area is 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 cross section of the terminal material on which the fired layer was formed by polishing the cross section by cross section polishing using an electron microscope (SEM) and observing at a magnification of 5000 From the image, 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 void was defined as the porosity.

(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。
(Thickness and thickness variation)
The film thickness and thickness variation of the fired layer are obtained by observing a cross section of the terminal material on which the fired layer is formed by polishing the cross section by cross section polishing using an electron microscope (SEM) at a magnification of 500 times The film thickness of the fired layer was arbitrarily measured at five places from the image obtained by the above, the average value of the film thickness at five places was taken as the film thickness, and the value of the standard deviation 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 baked layer on the outermost surface conformed to JCBA-T323, and the contact resistance at a load of 0.98 N was measured by a sliding method (1 mm) using a four-terminal contact resistance tester. First, after measuring the initial contact resistance immediately after the formation of the fired layer, as a heat treatment, the contact resistance was measured again after holding for 1000 hours in an air atmosphere at 200 ° C. using a thermostatic chamber.
As for the initial resistance value, those with less than 5 mΩ are regarded as “〇”, those with 5 mΩ or more and 10 mΩ or less are regarded as “Δ”, and those with more than 10 mΩ are regarded as “x”.
With regard to the contact resistance change rate, the change rate of the measured value after holding at 200 ° C for 1000 hours from the initial measurement is “◎” if less than 10%, “10% or more and less than 20%” A sample with 20% or more and less than 25% was designated as “Δ”, and one with 25% or more was designated as “X”.
The results are shown in Table 1.

Figure 2019099848
Figure 2019099848

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 substrate made of copper or copper alloy has all the initial resistance values. It was found that 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 to 70% by mass, and the component ratio of at least one of platinum and palladium is 30% by mass to 90% by mass Or less, in which 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, both the initial resistance value and the contact resistance change rate are “〇” This is especially true, and the contact reliability was 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 (5)

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ことを特徴とする銅端子材。   What is claimed is: 1. A copper terminal material characterized in that a sintered 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 substrate made of copper or copper alloy. 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%以上であることを特徴とする請求項1に記載の銅端子材。   In the fired layer, at least one component ratio of gold and silver is 10% by mass to 70% by mass, and at least one component ratio of platinum and palladium is 30% by mass to 90% by mass, and each of them The sum of a component ratio is 95 mass% or more, The copper terminal material of Claim 1 characterized by the above-mentioned. 前記焼成層の空隙率が20%以下であることを特徴とする請求項1又は2に記載の銅端子材。   The porosity of the said baking layer is 20% or less, The copper terminal material of Claim 1 or 2 characterized by the above-mentioned. 前記焼成層の膜厚は、0.3μm以上3.0μm以下であることを特徴とする請求項1から3のいずれか一項に記載の銅端子材。   The film thickness of the said baking layer is 0.3 micrometer or more and 3.0 micrometers or less, The copper terminal material as described in any one of Claim 1 to 3 characterized by the above-mentioned. 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を焼成して焼成層を形成することを特徴とする銅端子材の製造方法。   After applying a coating material containing at least one powder of at least one of gold and silver and at least one powder of at least one of platinum and palladium on a part of the surface of a substrate made of copper or copper alloy, the coating material applied C. to form a fired layer, and a method of manufacturing a copper terminal material.
JP2017229793A 2017-11-30 2017-11-30 Manufacturing method of copper terminal material Active JP7024358B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017229793A JP7024358B2 (en) 2017-11-30 2017-11-30 Manufacturing method of copper terminal material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2017229793A JP7024358B2 (en) 2017-11-30 2017-11-30 Manufacturing method of copper terminal material

Publications (2)

Publication Number Publication Date
JP2019099848A true JP2019099848A (en) 2019-06-24
JP7024358B2 JP7024358B2 (en) 2022-02-24

Family

ID=66976189

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2017229793A Active JP7024358B2 (en) 2017-11-30 2017-11-30 Manufacturing method of copper terminal material

Country Status (1)

Country Link
JP (1) JP7024358B2 (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4837184B1 (en) * 1969-07-30 1973-11-09
JPS5757808A (en) * 1980-09-25 1982-04-07 Nec Corp Production of electric contact
JPH0528868A (en) * 1991-07-22 1993-02-05 Daido Steel Co Ltd Electronic contact member and band material for it
JP2002198624A (en) * 2000-12-27 2002-07-12 Kyocera Corp Circuit board
JP2011192947A (en) * 2010-03-17 2011-09-29 Hitachi Cable Ltd Manufacturing method for sintered layer, and structure
WO2014077410A1 (en) * 2012-11-19 2014-05-22 田中貴金属工業株式会社 Method and device for producing silver-containing layer, silver-containing layer, and sliding contact material using silver-containing layer
JP2015067855A (en) * 2013-09-27 2015-04-13 株式会社茨城技研 Metal film forming method, and production method and production device of metal film forming product
JP2017082296A (en) * 2015-10-29 2017-05-18 三菱マテリアル株式会社 Method for forming metal film
JP2017095747A (en) * 2015-11-20 2017-06-01 株式会社 M&M研究所 Manufacturing method of metal film formation article

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4837184B1 (en) * 1969-07-30 1973-11-09
JPS5757808A (en) * 1980-09-25 1982-04-07 Nec Corp Production of electric contact
JPH0528868A (en) * 1991-07-22 1993-02-05 Daido Steel Co Ltd Electronic contact member and band material for it
JP2002198624A (en) * 2000-12-27 2002-07-12 Kyocera Corp Circuit board
JP2011192947A (en) * 2010-03-17 2011-09-29 Hitachi Cable Ltd Manufacturing method for sintered layer, and structure
WO2014077410A1 (en) * 2012-11-19 2014-05-22 田中貴金属工業株式会社 Method and device for producing silver-containing layer, silver-containing layer, and sliding contact material using silver-containing layer
JP2015067855A (en) * 2013-09-27 2015-04-13 株式会社茨城技研 Metal film forming method, and production method and production device of metal film forming product
JP2017082296A (en) * 2015-10-29 2017-05-18 三菱マテリアル株式会社 Method for forming metal film
JP2017095747A (en) * 2015-11-20 2017-06-01 株式会社 M&M研究所 Manufacturing method of metal film formation article

Also Published As

Publication number Publication date
JP7024358B2 (en) 2022-02-24

Similar Documents

Publication Publication Date Title
US9190322B2 (en) Method for producing a copper layer on a semiconductor body using a printing process
TWI409827B (en) Copper conductor paste, conductor circuit boards and electronic components
KR20130002980A (en) Method for manufacturing a metallized substrate
JP2009141292A (en) Electronic part having external terminal electrode and electronic supplies material mounted with the same, and method of manufacturing electronic part having external terminal electrode
JP2017155166A (en) Joining composition
Lall et al. Process Recipes for Additively Printed Copper-Ink Flexible Circuits using Direct Write Methods
JP6399494B2 (en) Method for producing metal film-formed product
JP7024358B2 (en) Manufacturing method of copper terminal material
JP6972978B2 (en) Manufacturing method of copper terminal material
JP6347385B2 (en) Copper material joining method
JP5962025B2 (en) Conductive composition and method for producing joined body
Yamaguchi et al. On-demand infrared laser sintering of gold nanoparticle paste for electrical contacts
US20130192873A1 (en) Structure body and electronic component and printed wiring board including the same
JP6488070B2 (en) Terminal fitting
JP2006128608A (en) Electronic part, method for manufacturing the same, chip resistor using the same, ferrite core and inductor
JP5213494B2 (en) Manufacturing method of ceramic substrate
JP6851810B2 (en) Manufacturing method of heat bonding material and electrical and electronic equipment
JP2019169714A (en) Capacitor and manufacturing method of the same
JP2020149770A (en) Metal plating terminal and manufacturing method thereof
JP6845444B1 (en) Joining material, manufacturing method of joining material and joining body
JP6442688B2 (en) Metal joining method
JP6825401B2 (en) Manufacturing method of copper terminal material with precious metal layer
JP6809265B2 (en) Manufacturing method of copper terminal material with precious metal layer
JP6794863B2 (en) Copper terminal material and its manufacturing method
JP2018129226A (en) Copper terminal material and method for manufacturing the same

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20200929

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20210524

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20210601

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20210721

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20211005

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20211015

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20220111

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20220124

R150 Certificate of patent or registration of utility model

Ref document number: 7024358

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150