JPH04329891A - Tin plated copper alloy material and its production - Google Patents
Tin plated copper alloy material and its productionInfo
- Publication number
- JPH04329891A JPH04329891A JP12673191A JP12673191A JPH04329891A JP H04329891 A JPH04329891 A JP H04329891A JP 12673191 A JP12673191 A JP 12673191A JP 12673191 A JP12673191 A JP 12673191A JP H04329891 A JPH04329891 A JP H04329891A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- tin
- plating layer
- plating
- alloy 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
Links
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 40
- 239000000956 alloy Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000007747 plating Methods 0.000 claims abstract description 97
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 31
- 229910005102 Ni3Sn Inorganic materials 0.000 claims abstract description 28
- 239000010949 copper Substances 0.000 claims description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 abstract description 9
- 238000002844 melting Methods 0.000 abstract description 7
- 230000008018 melting Effects 0.000 abstract description 7
- 239000010410 layer Substances 0.000 abstract 11
- 239000002344 surface layer Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 239000000463 material Substances 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000005476 soldering Methods 0.000 description 7
- 229910001369 Brass Inorganic materials 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000010951 brass Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910018082 Cu3Sn Inorganic materials 0.000 description 3
- 229910018471 Cu6Sn5 Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 229910007565 Zn—Cu Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、錫めっき銅合金材およ
びその製造方法に係り、より詳細には、例えば、端子・
コネクター等の電子材料部品に好適に用いられる半田付
け性に優れた錫めっき銅合金材およびその製造方法に関
する。[Field of Industrial Application] The present invention relates to a tin-plated copper alloy material and a method for manufacturing the same, and more specifically relates to a tin-plated copper alloy material and a method for manufacturing the same.
The present invention relates to a tin-plated copper alloy material with excellent solderability that is suitably used for electronic material parts such as connectors, and a method for manufacturing the same.
【０００２】0002
【従来の技術】錫めっき銅合金材は、端子・コネクター
をはじめ様々な電子部品に用いられている。錫めっきを
施す目的は、耐食性、良好な半田付け性を付与するため
である。また、接点材では、接触抵抗値を低く安定に保
つ目的をも持っている。BACKGROUND OF THE INVENTION Tin-plated copper alloy materials are used in various electronic parts including terminals and connectors. The purpose of tin plating is to provide corrosion resistance and good solderability. The contact material also has the purpose of keeping the contact resistance low and stable.
【０００３】従来、これらの錫めっき銅合金材の多くは
、銅合金材上に直接錫めっきを施すか、あるいは銅合金
材と錫めっきの間に銅下地めっきを施して製造されてい
た。Ｚｎを含む黄銅では、銅下地めっきが施されるが、
これは、Ｚｎが錫めっき中を短時間に粒界拡散し、錫め
っき層の表面に濃縮して半田付け性を劣化させることを
防ぐためである。Conventionally, most of these tin-plated copper alloy materials have been manufactured by directly applying tin plating on the copper alloy material or by applying copper underplating between the copper alloy material and the tin plating. Brass containing Zn is plated with a copper base, but
This is to prevent Zn from diffusing at grain boundaries in the tin plating in a short period of time, concentrating on the surface of the tin plating layer, and deteriorating solderability.
【０００４】しかし、銅下地めっき上に直接、錫めっき
を施すと、室温付近の温度においても、錫と銅が反応拡
散して、金属間化合物Ｃｕ６Ｓｎ５からなるη層ができ
る。また、約８０℃以上の環境に置かれると金属間化合
物Ｃｕ３Ｓｎからなるε層も成長する。これらの拡散は
非常に速く、１００〜２００℃で数時間から数十時間で
１〜２μｍ拡散する。However, when tin plating is applied directly onto the copper base plating, tin and copper react and diffuse even at temperatures around room temperature, forming an η layer made of the intermetallic compound Cu6Sn5. Furthermore, when placed in an environment of about 80° C. or higher, an ε layer made of an intermetallic compound Cu3Sn also grows. These diffusions are very fast, and they diffuse by 1 to 2 μm in several hours to several tens of hours at 100 to 200°C.
【０００５】これら金属間化合物は錫めっき材の特性に
悪影響を及ぼす。例えば、錫めっきとＣｕが反応拡散し
て脆いε層を厚く形成すると、曲げ加工時のめっき層の
剥離の原因となる。また、錫めっき層全体が金属間化合
物となり、純錫層がなくなると、半田付けが不可能にな
ったり、錫めっき層の表面にＣｕが拡散して銅の酸化物
をつくり、接触抵抗値が高くなったりする。[0005] These intermetallic compounds have an adverse effect on the properties of tin-plated materials. For example, if tin plating and Cu react and diffuse to form a thick brittle ε layer, this may cause peeling of the plating layer during bending. In addition, if the entire tin plating layer becomes an intermetallic compound and the pure tin layer disappears, soldering becomes impossible, and Cu diffuses into the surface of the tin plating layer to form copper oxide, which lowers the contact resistance value. It can get expensive.
【０００６】最近の、電気・電子部品の小型化、薄肉化
、および表面実装化の導入による半田付け方法の変化に
よって、部品の受ける熱影響はさらに厳しいものになっ
ている。そこで、従来の錫めっき銅合金材は、良好な半
田付け性や低く安定な接触抵抗値を満足できない場合が
発生するようになった。[0006] Recent changes in soldering methods due to the miniaturization and thinning of electrical and electronic components and the introduction of surface mounting have made the effects of heat on components even more severe. Therefore, conventional tin-plated copper alloy materials are sometimes unable to satisfy good solderability and low and stable contact resistance values.
【０００７】これを避けるための１つの対策として、錫
めっきを厚く施し、拡散の時間をかせぐ方法があるが、
錫めっき材のコストを高くするという問題がある。また
、錫めっきが厚いとスタンピングの際に端面に錫のバリ
（スタンピングのカス）が多く発生し、金型の寿命を短
くする問題があった。One measure to avoid this is to apply thick tin plating to allow time for diffusion.
There is a problem of increasing the cost of tin-plated materials. Further, if the tin plating is thick, a lot of tin burrs (stamping residue) will be generated on the end face during stamping, which will shorten the life of the mold.
【０００８】そこで、従来通りの薄い錫めっき層で、熱
影響に対して半田付け性および接触抵抗値の変化が小さ
い錫めっき銅合金材が望まれていた。[0008] Therefore, there has been a demand for a tin-plated copper alloy material that has a conventional thin tin plating layer and that exhibits small changes in solderability and contact resistance due to thermal effects.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、熱影響後の
半田付け性に優れる錫めっき銅合金材およびその製造方
法を提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a tin-plated copper alloy material that has excellent solderability after being affected by heat, and a method for manufacturing the same.
【００１０】0010
【課題を解決するための手段】上記課題を解決するため
の本発明の第１の要旨は、表面に、銅下地めっき層、厚
さが０．１〜０．４μｍの溶融して形成されたＮｉ３Ｓ
ｎ金属間化合物からなる中間層、錫めっき層が順次形成
されていることを特徴とする錫めっき銅合金材に存在す
る。[Means for Solving the Problems] A first aspect of the present invention for solving the above problems is to provide a copper base plating layer with a thickness of 0.1 to 0.4 μm formed on the surface by melting. Ni3S
It exists in a tin-plated copper alloy material characterized by sequentially forming an intermediate layer made of an n-intermetallic compound and a tin-plated layer.
【００１１】本発明の第２の要旨は、銅合金材の表面に
、銅下地めっき層、次いで厚さが０．０８〜０．３μｍ
のＮｉ中間めっき層を施し、さらにその上に錫めっき層
を施した後、該錫めっき層を溶融（リフロー）させるこ
とによって、銅下地めっき層と錫めっき層との中間に０
．１〜０．４μｍのＮｉ３Ｓｎ金属間化合物からなる中
間層を設けることを特徴とする錫めっき銅合金材の製造
方法に存在する。[0011] The second gist of the present invention is that a copper base plating layer is formed on the surface of the copper alloy material, followed by a copper base plating layer with a thickness of 0.08 to 0.3 μm.
After applying a Ni intermediate plating layer of
．． A method for manufacturing a tin-plated copper alloy material is provided, which is characterized by providing an intermediate layer made of a Ni3Sn intermetallic compound with a thickness of 1 to 0.4 μm.
【００１２】本発明の第３の要旨は、銅合金材の表面に
、銅下地めっき層、次いで厚さが０．０８〜０．３μｍ
のＮｉ中間めっき層を施した後、銅合金材を溶融した錫
中に浸漬し、溶融錫めっき層を形成すると同時に、銅合
金材と錫めっき層との中間に厚さが０．１〜０．４μｍ
のＮｉ３Ｓｎ金属間化合物からなる中間層を設けること
を特徴とする錫めっき銅合金材の製造方法に存在する。The third aspect of the present invention is that a copper base plating layer is formed on the surface of the copper alloy material, and then a copper base plating layer is formed on the surface of the copper alloy material, and then the thickness is 0.08 to 0.3 μm.
After applying the Ni intermediate plating layer, the copper alloy material is immersed in molten tin to form a hot-dip tin plating layer. .4μm
A method for manufacturing a tin-plated copper alloy material, which comprises providing an intermediate layer made of a Ni3Sn intermetallic compound.
【００１３】[0013]
【作用】発明の作用を本発明の詳細な構成とともに説明
する。[Operation] The operation of the invention will be explained together with the detailed structure of the invention.
【００１４】本発明では、銅下地めっきと錫めっき層と
の間に厚さが０．１〜０．４μｍのＮｉ３Ｓｎ層を設け
る。このＮｉ３Ｓｎ層が錫めっき層中への銅の拡散を防
ぎ、ひいては錫めっき層が金属間化合物に変化するのを
抑制する。Ｎｉ３Ｓｎ金属間化合物層中のＣｕの拡散速
度が錫めっき層中の拡散速度に比べ、きわめて遅いこと
を知見し、かかる知見に基づきＮｉ３Ｓｎ金属間化合物
を設ける構成としたものである。Ｎｉ３Ｓｎ金属間化合
物層層の存在によって、錫めっき層はＣｕとの金属間化
合物の生成を防ぎ純錫の部分を長期に保存することがで
きる。そして、純錫層を長期に渡って残存させることが
、良好な半田付け性、低い接触抵抗値を長期に保つこと
になるのである。In the present invention, a Ni3Sn layer having a thickness of 0.1 to 0.4 μm is provided between the copper underplating and the tin plating layer. This Ni3Sn layer prevents copper from diffusing into the tin plating layer and, in turn, suppresses the tin plating layer from changing into an intermetallic compound. It has been found that the diffusion rate of Cu in the Ni3Sn intermetallic compound layer is extremely slow compared to the diffusion rate in the tin plating layer, and based on this knowledge, a structure in which the Ni3Sn intermetallic compound is provided is provided. Due to the presence of the Ni3Sn intermetallic compound layer, the tin plating layer can prevent the formation of intermetallic compounds with Cu and can preserve the pure tin portion for a long time. By allowing the pure tin layer to remain for a long period of time, good solderability and low contact resistance can be maintained for a long period of time.
【００１５】以下により詳細に本発明をなすに際して得
た知見とともに作用を明らかにする。[0015] The knowledge obtained in making the present invention and its effects will be explained in more detail below.
【００１６】従来、Ｎｉ３Ｓｎ層のような金属間化合物
ができると曲げ加工によってめっき層が金属間化合物の
層と銅合金材の界面から剥離すると言われていた。従っ
て、Ｎｉ３Ｓｎ金属間化合物の生成を極力抑えることが
従来から行われていた。しかし、経時的な拡散によって
できる金属間化合物の場合とは異なり、錫の融点以上で
溶融してできた金属間化合物の場合は、界面に拡散によ
る欠陥も少なく、密着性に優れていることを見い出した
。Conventionally, it has been said that when an intermetallic compound such as a Ni3Sn layer is formed, the plating layer peels off from the interface between the intermetallic compound layer and the copper alloy material due to bending. Therefore, conventional efforts have been made to suppress the formation of Ni3Sn intermetallic compounds as much as possible. However, unlike the case of intermetallic compounds formed by diffusion over time, intermetallic compounds formed by melting above the melting point of tin have fewer defects at the interface due to diffusion and have excellent adhesion. I found it.
【００１７】ただ、溶融してできた金属間化合物を銅下
地めっき層と錫めっき層との間に介在せしめた場合であ
っても必ずしも密着性に優れない場合もあり、その原因
を鋭意探求したところ、金属間化合物からなる層の厚み
が密着性に影響を与えていることをも突き止めた。However, even when intermetallic compounds formed by melting are interposed between the copper base plating layer and the tin plating layer, adhesion may not always be excellent, and we have diligently investigated the cause of this. However, it was also discovered that the thickness of the intermetallic compound layer affected adhesion.
【００１８】このように、Ｎｉ３Ｓｎの金属間化合物か
らなる層は、それを錫の融点以上の温度で生成し、その
厚さを一定の範囲に制御した場合、めっき剥離の悪影響
を与えずに錫めっき層の合金化を防ぐという特徴をもつ
ことを明らかにした。これによって、熱的にもまた経時
的にも安定した半田付け性を有する錫めっき銅合金材及
びその製造方法を開発するにいたったのである。[0018] As described above, when a layer made of an intermetallic compound of Ni3Sn is formed at a temperature higher than the melting point of tin and its thickness is controlled within a certain range, tin can be formed without causing any adverse effects of plating peeling. It was revealed that this material has the characteristic of preventing alloying of the plating layer. This led to the development of a tin-plated copper alloy material that has stable solderability both thermally and over time, and a method for manufacturing the same.
【００１９】密着性に優れた金属間化合物とするには、
その厚さを０．１μｍ以上にする。Ｎｉ３Ｓｎ層の厚さ
を０．１μｍとしたのは、銅の錫中への拡散を防ぐには
、０．１μｍ以上のＮｉ３Ｓｎ層が必要だからである。
また、０．４μｍ以下としたのは、それを越えても銅の
拡散防止の効果に大差は無いためである。また、０．４
μｍを越えてＮｉ３Ｓｎ層が成長すると、曲げ加工時に
曲げの応力が大きくなって、Ｎｉ３Ｓｎ層が銅合金の界
面から剥離する。さらに、０．４μｍを越え錫めっき層
が薄いとその層の大部分が合金層になり純錫層が薄くな
り、ひいては半田付け性、接触抵抗性が悪くなる。これ
は、加熱によって錫めっき層中にＮｉが拡散して錫めっ
き表面に達し、ニッケルの酸化物を生成する為であると
推定される。また、金属間化合物層が０．４μｍを越え
た厚さになるとめっき材をスタンピングする際に、ダイ
スの寿命を短くする原因にもなる。よって、Ｎｉ３Ｓｎ
層の厚さは０．１〜０．４μｍとした。[0019] In order to obtain an intermetallic compound with excellent adhesion,
The thickness is set to 0.1 μm or more. The reason why the thickness of the Ni3Sn layer is set to 0.1 μm is that a Ni3Sn layer of 0.1 μm or more is required to prevent copper from diffusing into tin. The reason why the thickness is set to 0.4 μm or less is that there is no significant difference in the effect of preventing copper diffusion even if the thickness exceeds 0.4 μm. Also, 0.4
When the Ni3Sn layer grows beyond μm, bending stress increases during bending, and the Ni3Sn layer peels off from the interface of the copper alloy. Furthermore, if the tin plating layer is thinner than 0.4 μm, most of the layer becomes an alloy layer, and the pure tin layer becomes thinner, resulting in poor solderability and contact resistance. This is presumed to be because Ni diffuses into the tin plating layer due to heating and reaches the tin plating surface, producing nickel oxide. Further, if the thickness of the intermetallic compound layer exceeds 0.4 μm, it may shorten the life of the die when stamping a plating material. Therefore, Ni3Sn
The thickness of the layer was 0.1 to 0.4 μm.
【００２０】銅下地錫めっきの厚さは限定しないが、実
際には、０．３〜１．０μｍが好ましい。素材からのＺ
ｎの錫めっき層中への拡散を防ぎ、半田付け性を良好に
保つには、０．３μｍの銅めっき層で十分だからである
。また、銅めっき層の厚さが１μｍ以上厚くても錫めっ
き層中へのＺｎの拡散防止効果に大差がないからである
。Although the thickness of the tin plating on the copper base is not limited, it is actually preferably 0.3 to 1.0 μm. Z from material
This is because a copper plating layer of 0.3 μm is sufficient to prevent diffusion of n into the tin plating layer and maintain good solderability. Further, even if the copper plating layer is thicker by 1 μm or more, there is no significant difference in the effect of preventing Zn from diffusing into the tin plating layer.
【００２１】また、銅めっきの厚さは、コストやスタン
ピング時のバリやカスの発生を考慮すると薄い方が望ま
しい。しかし、一方、耐熱剥離性、半田付け性の観点か
らは厚い方が望ましい。詳細は、めっき材の用途に応じ
て決定すればよい。しかし、めっきを行なってから部品
に加工され、機器に実装される際の半田付けを行なうま
での期間をおよそ１年とすると、その期間、良好な半田
付け性を保持するためには、０．３μｍ以上とする事が
好ましい。[0021] Furthermore, the thickness of the copper plating is desirably thinner in consideration of cost and generation of burrs and dregs during stamping. However, on the other hand, from the viewpoint of heat-resistant peelability and solderability, the thicker the layer is, the more desirable it is. The details may be determined depending on the use of the plating material. However, if the period from plating to soldering when processed into parts and mounted on equipment is approximately one year, in order to maintain good solderability during that period, 0. The thickness is preferably 3 μm or more.
【００２２】次に、製造方法について説明する。Next, the manufacturing method will be explained.
【００２３】本発明では、銅合金材の表面にまず銅下地
めっきを施し、この銅下地めっき上にニッケルめっきを
施し、さらに錫めっきを施す。錫めっきを施す方法は、
■銅合金材に電気めっきを施した後にめっき層を溶融処
理するリフローめっき法、■銅合金材を溶解錫の中に浸
漬して錫層を設ける溶融めっき法のいずれでもよい。前
者では、電気めっき皮膜を溶融させる時に溶融した錫め
っきとニッケルめっきとがＮｉ３Ｓｎ層をつくる。溶融
めっきの場合も同様にＮｉ３Ｓｎ層をつくる。すなわち
、リフローめっきでは、光沢を付与するリフロー工程と
ニッケルめっきを化合物層に変化させる工程とを同時に
行なうものである。また、溶融めっきでは、錫層を設け
る工程をニッケルめっきを化合物層に変化させる工程と
を同時に行なうものである。In the present invention, the surface of the copper alloy material is first plated with copper undercoating, then nickel plating is applied on the copper underplating, and then tin plating is applied. The method of applying tin plating is
(2) A reflow plating method in which a copper alloy material is electroplated and then the plating layer is melt-treated; (2) A hot-dip plating method in which a copper alloy material is immersed in molten tin to form a tin layer. In the former case, when the electroplated film is melted, the molten tin plating and nickel plating form a Ni3Sn layer. In the case of hot-dip plating, a Ni3Sn layer is similarly formed. That is, in reflow plating, a reflow process for imparting gloss and a process for converting nickel plating into a compound layer are performed simultaneously. Furthermore, in hot-dip plating, the step of providing a tin layer and the step of converting nickel plating into a compound layer are performed simultaneously.
【００２４】ニッケルのめっきの厚さを０．０８μｍ以
上としたのは、それよりも薄いと生成するＮｉ３Ｓｎ層
の厚さが０．１μｍ未満となり、ＣｕのＳｎめっき中へ
の拡散防止効果が不十分になるからである。また、０．
３μｍ以下としたのは、０．３μｍを越えるとＮｉ３Ｓ
ｎ層の厚さが０．４μｍを越え、上述した問題が生じる
からである。さらに、ニッケルめっき層が完全にはＮｉ
３Ｓｎ金属間化合物層にならずに残存し、錫とニッケル
の反応拡散が進行して、欠陥が多く、脆い金属間化合物
層をつくる恐れがあるからである。よって、Ｎｉめっき
の厚さは０．０８〜０．３μｍとした。The reason why the thickness of the nickel plating is set to 0.08 μm or more is because if it is thinner, the thickness of the Ni3Sn layer formed will be less than 0.1 μm, and the effect of preventing Cu from diffusing into the Sn plating will be insufficient. Because it will be enough. Also, 0.
The reason for setting it below 3μm is that if it exceeds 0.3μm, Ni3S
This is because the thickness of the n-layer exceeds 0.4 μm, causing the above-mentioned problem. Furthermore, the nickel plating layer is completely covered with Ni.
This is because there is a risk that the 3Sn intermetallic compound layer may remain without becoming a 3Sn intermetallic compound layer, and the reaction and diffusion of tin and nickel may proceed, creating a brittle intermetallic compound layer with many defects. Therefore, the thickness of the Ni plating was set to 0.08 to 0.3 μm.
【００２５】なお、Ｎｉ３Ｓｎ層の厚さの制御は、リフ
ローめっきの場合は、Ｎｉめっきの厚さないしリフロー
温度及び時間を制御することにより、溶融めっきの場合
は、Ｎｉめっきの厚さないしめっき液の溶融温度及びめ
っき時間を制御することにより行えばよい。The thickness of the Ni3Sn layer can be controlled by controlling the thickness of the Ni plating or the reflow temperature and time in the case of reflow plating, or by controlling the thickness of the Ni plating and the reflow temperature and time in the case of hot-dip plating. This can be done by controlling the melting temperature and plating time.
【００２６】なお、本発明では、母材としてＺｎを含む
銅合金（例えば、丹銅や黄銅）を用いた場合に特に顕著
な効果が得られるが、それ以外の銅あるいは銅合金を用
いることも可能である。[0026] In the present invention, particularly remarkable effects can be obtained when a copper alloy containing Zn (for example, red copper or brass) is used as the base material, but other copper or copper alloys may also be used. It is possible.
【００２７】[0027]
【実施例】以下に本発明の実施例を説明する。[Examples] Examples of the present invention will be described below.
【００２８】本例では、母材として、丹銅のＣ２１００
（５．１ｗｔ％Ｚｎ−Ｃｕ）、黄銅のＣ２６００（３０
．５ｗｔ％Ｚｎ−Ｃｕ）、Ｃ２６８０（３５．２ｗｔ％
ｚｎ−Ｃｕ）を用いた。In this example, red copper C2100 is used as the base material.
(5.1 wt% Zn-Cu), brass C2600 (30
．． 5wt% Zn-Cu), C2680 (35.2wt%
zn-Cu) was used.
【００２９】この銅合金の表面に、常法により銅下地め
っきを０．８μｍの厚さに形成した。[0029] On the surface of this copper alloy, a copper underplating was formed to a thickness of 0.8 μm by a conventional method.
【００３０】次いで、この銅下地めっき上に常法により
、ニッケルめっきを表１に示す厚さに形成した。[0030]Next, nickel plating was formed on this copper base plating by a conventional method to the thickness shown in Table 1.
【００３１】次に、表１のＮｏ．１，Ｎｏ．６，Ｎｏ．
１３〜Ｎｏ．１５については溶融めっきを行い、それ以
外に付いてはリフローめっきを行った。Next, No. 1 in Table 1. 1, No. 6, No.
13~No. No. 15 was subjected to hot-dip plating, and the others were subjected to reflow plating.
【００３２】めっき条件は下記の通りである。[0032] The plating conditions are as follows.
【００３３】
以上のようにして形成したしためっきにつき、錫め
っきの厚さとＮｉ３Ｓｎ層の厚さを測定した。その結果
を表１に示す。[0033] Regarding the plating formed as described above, the thickness of the tin plating and the thickness of the Ni3Sn layer were measured. The results are shown in Table 1.
【００３４】また、これらの錫めっき銅合金材を、２２
０℃で５分および１０分の熱処理を行った後、接触抵抗
、半田付け性及び密着性を評価した。評価方法は下記の
通りである。なお、上記熱処理条件は、最近のコネクタ
ーの表面実装化にともない増加しているリフロー半田付
け方法を考慮したものである。[0034] Furthermore, these tin-plated copper alloy materials were
After heat treatment was performed at 0° C. for 5 and 10 minutes, contact resistance, solderability, and adhesion were evaluated. The evaluation method is as follows. Note that the above heat treatment conditions take into consideration the reflow soldering method, which is increasing in number with the recent trend of surface mounting connectors.
【００３５】（半田付け試験条件）
半田組成：Ｓｎ／Ｐｂ＝６／４
半田温度：２３０±５℃
フラックス：ロジン系非活性フラックス半田付けの評価
は、半田付け後に半田の付着面積が８５％以上を“良好
”とし、それ以下を“不良”とした。(Soldering test conditions) Solder composition: Sn/Pb=6/4 Solder temperature: 230±5°C Flux: Rosin-based inert flux Soldering was evaluated when the solder adhesion area was 85% or more after soldering. was defined as "good", and anything less than that was defined as "bad".
【００３６】（接触抵抗測定条件）
荷重：５０ｇｆ（測定時）
電流値：２０ｍＡ
接触抵抗は、荷重を０〜５０ｇｆに変化させながら純金
のプローブを試料表面で往復スライドさせ、５０ｇｆの
荷重がかかった時の値を測定した。(Contact resistance measurement conditions) Load: 50 gf (during measurement) Current value: 20 mA Contact resistance was determined by sliding a pure gold probe back and forth on the sample surface while changing the load from 0 to 50 gf, and applying a load of 50 gf. The value at the time was measured.
【００３７】（密着性試験）密着性は１５０℃で５００
時間熱処理した後、これらの材料に９０°繰り返し曲げ
を２回行い、曲げ部表面を実体顕微鏡で観察し、めっき
層の剥離の有無を確認した。(Adhesion test) Adhesion was 500 at 150°C.
After being heat-treated for a period of time, these materials were repeatedly bent at 90° twice, and the surfaces of the bent portions were observed using a stereomicroscope to confirm the presence or absence of peeling of the plating layer.
【００３８】半田付け性、接触抵抗の評価及び密着性試
験の結果を表１に示す。Table 1 shows the results of solderability, contact resistance evaluation, and adhesion test.
【００３９】その結果、金属間化合物Ｎｉ３Ｓｎ層の厚
さが０．１μｍ以上で０．４μｍ以下の時（ＮＯ．１〜
Ｎｏ．９、実施例）、半田付け性は良好で、接触抵抗値
が低く保たれた。これは、Ｎｉ３Ｓｎ層が、Ｃｕの拡散
を抑制し、Ｃｕ６Ｓｎ５からなるη層、Ｃｕ３Ｓｎから
なるε層の成長を防止したためである。As a result, when the thickness of the intermetallic compound Ni3Sn layer was 0.1 μm or more and 0.4 μm or less (No. 1 to
No. 9. Example), the solderability was good and the contact resistance value was kept low. This is because the Ni3Sn layer suppressed the diffusion of Cu and prevented the growth of the η layer made of Cu6Sn5 and the ε layer made of Cu3Sn.
【００４０】Ｎｏ．１０〜Ｎｏ．１８はいずれもＮｉ３
Ｓｎ層の厚さが０．４μｍを越えているため、密着性試
験でＮｉ３Ｓｎ層の剥離が生じた。[0040]No. 10~No. All 18 are Ni3
Since the thickness of the Sn layer exceeded 0.4 μm, peeling of the Ni3Sn layer occurred in the adhesion test.
【００４１】また、従来のように、金属間化合物Ｎｉ３
Ｓｎ層が無い場合（Ｎｏ．２０，Ｎｏ．２１）、あるい
はあっても０．１μｍより薄い場合（Ｎｏ．１９）は、
錫中にＣｕ６Ｓｎ５からなるη層、Ｃｕ３Ｓｎからなる
ε層が成長し、錫めっき層が早期に金属間化合物に変化
してしまい密着性が悪かった。[0041] Also, as conventionally, the intermetallic compound Ni3
If there is no Sn layer (No. 20, No. 21), or if it is thinner than 0.1 μm (No. 19),
An η layer made of Cu6Sn5 and an ε layer made of Cu3Sn grew in the tin, and the tin plating layer quickly changed to an intermetallic compound, resulting in poor adhesion.
【００４２】以上の実施例の結果から、金属間化合物Ｎ
ｉ３Ｓｎ層の厚さは０．１〜０．４μｍが必要であり、
その厚さの金属間化合物層を得るためには、Ｎｉめっき
層を０．０８〜０．３μｍ施すことが必要であることが
明らかになった。From the results of the above examples, it is clear that the intermetallic compound N
The thickness of the i3Sn layer needs to be 0.1 to 0.4 μm,
It has become clear that in order to obtain an intermetallic compound layer of that thickness, it is necessary to apply a Ni plating layer of 0.08 to 0.3 μm.
【００４３】[0043]
【発明の効果】本発明によって、優れた半田付け性、熱
的に安定な接触抵抗値を有する錫めっき黄銅あるいは丹
銅材を製造することができる。これらの錫めっき銅合金
材は、端子・コネクター等の電気・電子部品の半田付け
性および接触抵抗特性を向上させることになり、機器の
信頼性を高めるることに貢献できる。According to the present invention, a tin-plated brass or red copper material having excellent solderability and thermally stable contact resistance can be produced. These tin-plated copper alloy materials improve the solderability and contact resistance characteristics of electrical and electronic components such as terminals and connectors, and can contribute to increasing the reliability of equipment.
【００４４】[0044]
【表１】[Table 1]
Claims (3)
１〜０．４μｍの溶融して形成されたＮｉ３Ｓｎ金属間
化合物からなる中間層、錫めっき層が順次形成されてい
ることを特徴とする錫めっき銅合金材。Claim 1: The surface has a copper underplating layer with a thickness of 0.
A tin-plated copper alloy material, characterized in that an intermediate layer made of a melted Ni3Sn intermetallic compound having a thickness of 1 to 0.4 μm and a tin plating layer are successively formed.
次いで厚さが０．０８〜０．３μｍのＮｉ中間めっき層
を施し、さらにその上に錫めっき層を施した後、該錫め
っき層を溶融（リフロー）させることによって、銅下地
めっき層と錫めっき層との中間に０．１〜０．４μｍの
Ｎｉ３Ｓｎ金属間化合物からなる中間層を設けることを
特徴とする錫めっき銅合金材の製造方法。[Claim 2] A copper base plating layer on the surface of the copper alloy material,
Next, a Ni intermediate plating layer with a thickness of 0.08 to 0.3 μm is applied, and a tin plating layer is further applied thereon, and then the tin plating layer is melted (reflowed) to bond the copper base plating layer and the tin plating layer. A method for manufacturing a tin-plated copper alloy material, comprising providing an intermediate layer of 0.1 to 0.4 μm of Ni3Sn intermetallic compound between the plating layer and the plating layer.
次いで厚さが０．０８〜０．３μｍのＮｉ中間めっき層
を施した後、銅合金材を溶融した錫中に浸漬し、溶融錫
めっき層を形成すると同時に、銅合金材と錫めっき層と
の中間に厚さが０．１〜０．４μｍのＮｉ３Ｓｎ金属間
化合物からなる中間層を設けることを特徴とする錫めっ
き銅合金材の製造方法。[Claim 3] A copper base plating layer on the surface of the copper alloy material,
Next, after applying a Ni intermediate plating layer with a thickness of 0.08 to 0.3 μm, the copper alloy material is immersed in molten tin to form a molten tin plating layer, and at the same time, the copper alloy material and the tin plating layer are 1. A method for manufacturing a tin-plated copper alloy material, comprising providing an intermediate layer made of a Ni3Sn intermetallic compound with a thickness of 0.1 to 0.4 μm between the two layers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12673191A JP2801793B2 (en) | 1991-04-30 | 1991-04-30 | Tin-plated copper alloy material and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12673191A JP2801793B2 (en) | 1991-04-30 | 1991-04-30 | Tin-plated copper alloy material and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04329891A true JPH04329891A (en) | 1992-11-18 |
| JP2801793B2 JP2801793B2 (en) | 1998-09-21 |
Family
ID=14942489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12673191A Expired - Lifetime JP2801793B2 (en) | 1991-04-30 | 1991-04-30 | Tin-plated copper alloy material and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2801793B2 (en) |
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| EP4108810A4 (en) * | 2020-02-19 | 2023-08-09 | Senju Metal Industry Co., Ltd. | Metal body, fitting-type connection terminal, and metal body forming method |
| KR20230091104A (en) | 2020-10-20 | 2023-06-22 | 세이렌가부시끼가이샤 | Conductive film with excellent solder wettability |
| CN114990651A (en) * | 2022-04-29 | 2022-09-02 | 沈阳飞机工业（集团）有限公司 | Multiple electroplating process method for copper plating, cadmium plating and tin plating |
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| JP2801793B2 (en) | 1998-09-21 |
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