JP3519727B1 - Connector terminal and connector having the same - Google Patents

Abstract

An object of the present invention is to provide a connector terminal that has excellent heat resistance and corrosion resistance and has excellent heat resistance and corrosion resistance without a surface metal layer peeling off, and a connector having the same. SOLUTION: In the connector terminal of the present invention, a ruthenium layer is formed on the entire surface or a portion on a conductive substrate, and Au, Ag, Pd, or the like is formed on the entire surface or a portion on the ruthenium layer.
A surface metal layer made of at least one metal selected from the group consisting of Rh, Co, Ni, In, and Sn or an alloy containing at least one of these metals is formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a connector terminal widely used for connection in electric, electronic products, semiconductor products, automobile parts and the like, and more particularly to heat resistance, corrosion resistance and high hardness. The present invention relates to a connector terminal suitable for each required application and a connector having the same.

[0002]

2. Description of the Related Art Conventionally, various connector terminals have been used in applications such as electric and electronic products, semiconductor products and automobile parts. In particular, in applications where contact reliability is required, a connector terminal having a structure in which a Ni layer is formed on a conductive substrate and a thin gold layer is formed thereon is often used as such a connector terminal. It was
However, in this structure, since the hardness of both the Ni layer and the gold layer is relatively low, there is a problem that the gold layer is easily scraped or peeled off when the connector is repeatedly inserted and removed, which is a problem particularly when used at high temperature. Was there. This problem,
Not only the appearance is damaged, but the gold layer peels off
When the i layer appears on the surface, the Ni layer is easily oxidized and the contact electric resistance (hereinafter, simply referred to as contact resistance) becomes very high, which is a fatal problem. In order to solve this problem, it is conceivable to form a thick gold layer, but thickening the gold layer not only increases the cost but also increases the contact friction at the time of insertion / removal of the connector, impairing the insertion / removal property and the gold layer itself. However, this method has not been able to solve the problem, because it becomes more prone to wear.

On the other hand, in the connector terminal having the above structure in which the Ni layer and the gold layer are formed on the conductive substrate, the Ni layer is used.
There is also a problem that a pinhole is easily generated in the layer, and the conductive substrate and the gold layer are in direct contact with each other in this pinhole, so that electrical corrosion occurs due to the difference in ionization tendency between the two. This problem was particularly remarkable when the conductive substrate was copper or a copper alloy.

Incidentally, although a few terminals have recently been proposed as those used as such connector terminals (Patent Documents 1 and 2), those which directly solve the above problems are still unknown. Absent.

[0005]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-152385

[0006]

[Patent Document 2] Japanese Patent Laid-Open No. 2000-222960

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation, and an object of the present invention is that the surface layer is not peeled off and is excellent in insertability and detachability, as well as heat resistance and corrosion resistance. To provide a connector terminal having high hardness and the like and a connector having the same.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to solve the above-mentioned problems, and found that the metal layer has improved insertability, heat resistance and corrosion resistance while maintaining excellent contact resistance. For this reason, it was found that not only the surface metal layer but also the layer existing as a lower layer is important, and the present invention was finally completed by continuing the research based on this finding.

That is, the connector terminal of the present invention is made of Ni, Cu, Ag on the entire surface or part of the conductive substrate.
At least one metal selected from the group or these gold
At least an underlayer made of an alloy containing at least one genus
A ruthenium layer is formed on the entire surface or part of the underlayer, and is made of Ag, Rh , Co, Ni, In, Sn on the entire surface or part of the ruthenium layer. At least one metal or A selected from the group
Is it a group consisting of u, Ag, Rh, Co, Ni, In and Sn?
It is characterized in that a surface metal layer made of an alloy containing at least one kind of metal selected from the above is formed. By locating the ruthenium layer below the surface metal layer in this manner, it is possible to effectively prevent the surface metal layer from being worn or peeled by the interaction between the ruthenium layer and the surface metal layer. In addition to the excellent contact resistance of the surface metal layer, excellent insertion / removal performance can be obtained, and pinholes can be effectively prevented.
As a result, we have succeeded in dramatically improving quality such as high hardness, heat resistance, and corrosion resistance.

Further, the connector terminal of the present invention is characterized in that two or more surface metal layers having different compositions are formed. This makes it possible to expand the range in which the connector terminals are used to a wider range.

Further, the connector terminal of the present invention comprises, between the conductive substrate and the ruthenium layer, at least one metal selected from the group consisting of Ni, Cu and Ag or an alloy containing at least one of these metals. It is characterized in that at least one underlayer is formed. Although the ruthenium layer itself has a high hardness, it also has a large stress, so that the ruthenium layer itself may peel off depending on the type of the conductive substrate. It is the formation of strata.

On the other hand, in the present invention, the underlayer, the ruthenium layer and the surface metal layer are formed by a plating method using any of a barrel plating apparatus, a hook plating apparatus or a continuous plating apparatus. I am trying. This makes it possible to form these layers extremely efficiently.

The connector of the present invention has the connector terminal described in any of the above. As a result, it is possible to obtain a connector having excellent contact resistance, insertability, high hardness, heat resistance, and corrosion resistance, and extremely high reliability.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION <Conductive Substrate> The conductive substrate used in the present invention may be any conventionally known conductive substrate used for electric, electronic products, semiconductor products, automobile parts and the like. Can also be used.
For example, copper alloy materials such as copper (Cu), phosphor bronze, brass, beryllium copper, titanium copper, nickel silver (Cu, Ni, Zn), iron (Fe), Fe-Ni alloys, iron alloys such as stainless steel. Examples of such materials include nickel-based materials and copper patterns on various substrates. The shape of the conductive substrate is not limited to a planar shape such as a tape shape, but includes a three-dimensional shape such as a press-molded product, and any other shape may be used. Absent.

<Ruthenium Layer> The ruthenium layer of the present invention is formed on the entire surface or a portion of the conductive substrate, which will be described later, on the entire surface or a portion thereof.
It is made of ruthenium (Ru) alone or an alloy containing ruthenium. Here, as the alloy containing ruthenium, an alloy containing palladium (Pd) or nickel (Ni) in an amount of 30 mass% or less can be mentioned. Usually, ruthenium itself has high hardness and excellent corrosion resistance, so it is not necessary to use it by alloying it, but as described below, cost should be prioritized over stress reduction or strong corrosion resistance. In such a case, it may be preferable to use it as an alloy. Such a ruthenium layer has a thickness of 0.05 to 1.5 μm.
m, preferably 0.2 to 1.0 μm, with ruthenium metal alone or an alloy thereof as an underlayer on a conductive substrate.
It is formed by plating on top . The formation of the ruthenium layer on the portion on the conductive substrate (underlayer) means that it is formed on only one of the front and back surfaces of the conductive substrate and is formed on only a specific portion of those surfaces. As a forming method thereof, a conventionally known method such as a plating bath liquid level adjusting method, a masking method, a mechanical mask method, a belt method and a brush method can be applied. When the thickness of such a ruthenium layer is less than 0.05 μm, the interaction with the surface metal layer described later cannot be sufficiently exerted, and when it exceeds 1.5 μm, the stress of the ruthenium layer itself is increased. It is not preferable because it may become too large and may be peeled off from the conductive substrate or the ruthenium layer itself may be cracked. The ruthenium layer has high hardness and excellent oxidation resistance, and even if it is oxidized, its oxide shows a high conductivity of 10 ⁻⁶ S / m. Since the electric conductivity of is ^{11 11} S / m), it is considered that these synergistically act to highly interact with the surface metal layer described later.

<Surface Metal Layer> The surface metal layer of the present invention has a central function of imparting conductivity to the connector terminal, and is formed on the entire surface or a part of the ruthenium layer. , Ag, R
at least one metal selected from the group consisting of h 3 , Co, Ni, In, and Sn , or Au, Ag, Rh, Co, N
At least one selected from the group consisting of i, In, and Sn
It is composed of an alloy containing at least one of the above metals. In addition, two or more surface metal layers having different compositions can be formed. here,
The composition of the alloy is not particularly limited as long as it contains at least one of the metals listed above. For example, 50% by mass or more of at least one of the above metals 9
9.99 mass% or less, preferably 50 mass% or more 99.
9 mass% or less, more preferably 50 mass% or more 99.
The thing containing 8 mass% or less can be mentioned. A preferable example of such an alloy is a gold alloy. This is because among the above-mentioned metals, Rh has a high hardness per se and has little merit to be used as an alloy from the viewpoint of hardness, whereas gold (Au) itself is soft and alloyed in order to obtain a high hardness. It is preferable to do so. As such a gold alloy, cobalt (C
o), alloys with metals such as nickel (Ni), indium (In) and the like, and the content of gold (Au) is within the above range. In the case of forming two or more surface metal layers having different compositions from each other, for example, a gold alloy layer as described above is formed at an arbitrary portion on the ruthenium layer, which is different from that. Tin (Sn) or tin alloy (eg Sn-A)
g alloy, Sn-Cu alloy, Sn-Pb alloy, Sn-Zn
Alloys, Sn-Bi alloys, etc.). In this case, the gold alloy layer mainly exerts the action of imparting conductivity as described above, and the tin or tin alloy layer plays a role of soldering. Such a surface metal layer is usually 0.001 to 2 μm, preferably 0.1
Formed by plating the metal or alloy to a thickness of .about.0.5 .mu.m on the ruthenium layer. 0.00
When it is less than 1 μm, excellent contact resistance may not be obtained, while when it exceeds 2 μm, not only the cost becomes high but also interaction with the ruthenium layer is not exhibited, which is not preferable. However, when the surface metal layer is formed for the purpose of soldering as described above, the thickness of the surface metal layer should be 0.
It should be 5 to 10 μm. As a method of forming the surface metal layer on the portion on the ruthenium layer, a conventionally known method such as a plating bath liquid level adjusting method, a masking method, a mechanical mask method, a belt method, and a brush method can be applied.

<Underlayer> The underlayer of the present invention is formed because the above ruthenium layer may be easily peeled off depending on the type of the conductive substrate. Usually, the ruthenium layer hardly peels off by its own stress when the conductive substrate is made of a nickel-based material, but when the conductive substrate is made of a material other than the nickel-based material May be easily peeled off, and in such a case, it is necessary to form the underlayer. That is, the underlayer has a function of preventing peeling of the ruthenium layer. Therefore, the underlayer is formed between the conductive substrate and the ruthenium layer (that is, as a lower layer of the ruthenium layer), and Ni, C
A layer made of at least one metal selected from the group consisting of u and Ag or an alloy containing at least one of these metals, and is formed as at least one layer (that is, as a single layer or multiple layers). The composition of the alloy here is not particularly limited as long as it contains at least one of the above metals. For example, a material containing at least 50% by mass of at least one of the above metals can be mentioned.
Further, when such an underlayer is formed as a plurality of layers, it is preferable to determine the type and thickness of the metal or alloy forming each layer in consideration of the thickness of the ruthenium layer and the type of conductive substrate. . For example, when the conductive substrate is a copper alloy-based material, a thickness of 0.05 to 5 is applied on the conductive substrate.
It is preferable to form a first underlayer made of Ni having a thickness of μm and further forming a second underlayer made of Ag having a thickness of 0.05 to 3 μm on the first underlayer. When the conductive substrate is an iron-based material or brass, a first underlayer made of Cu having a thickness of 0.05 to 5 μm is formed on the conductive substrate, and a first underlayer having a thickness of 0.
It is preferable to form a second underlayer made of Ni having a thickness of 05 to 2 μm. As described above, the underlayer is usually a single layer or a plurality of layers and each metal or alloy is plated on the conductive substrate so that the thickness is 0.05 to 7 μm, preferably 0.8 to 4.0 μm. Can be formed. When the thickness of the underlayer is less than 0.05 μm, it may not be possible to prevent peeling of the ruthenium layer, while when it exceeds 7 μm, not only the cost increases but it becomes economically disadvantageous, and the time-dependent It is not preferable because the thickness of the conductive substrate is changed, the dimensional stability is lost, and the elasticity of the conductive substrate itself is lost.

<Connector Terminal> The connector terminal of the present invention has a structure in which the above layers are formed on a conductive substrate. As long as it has such a structure, the shape and configuration of the connector terminal itself are not particularly limited.

<Connector> The connector of the present invention has the above connector terminal. As long as it has such a connector terminal in terms of its structure, it is not limited to an ordinary connector but includes a pattern on a circuit board. As described above, the connector of the present invention is widely used in, for example, electric parts, electronic parts, semiconductor parts, automobile parts, and the like, and as long as the connector is insertable and removable and is intended for electrical connection. , It doesn't matter what shape it is.

<Manufacturing Apparatus> The underlayer, ruthenium layer and surface metal layer of the present invention are usually formed by a plating method as described above. Particularly, the plating apparatus is a barrel plating apparatus, a hook plating apparatus or It is preferably carried out by using any of continuous plating equipment. By using these devices, the connector terminals can be manufactured extremely efficiently. Here, the barrel plating device is a device for individually plating connector terminals one by one, and the continuous plating device is a device for continuously plating a plurality of connector terminals at once, and a hook plating device. Is a device located in the middle of the former two and having medium-scale manufacturing efficiency. These devices are well known in the plating industry, and any structure can be used as long as the structure itself is known.

[0021]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

Reference Example 1 This reference example relates to a connector terminal in which a ruthenium layer and a surface metal layer are formed in this order on a conductive substrate. Hereinafter, description will be given with reference to FIG.

First, the conductive substrate 101 has a thickness of 0.1.
70m for continuous connector terminal shape by pressing nickel tape-shaped nickel into the shape of connector terminal
It was cut to a length of m. After the cutting, 55 g / l of activator (trade name: ESCREEN 30, manufactured by Okuno Chemical Industry Co., Ltd.)
Degreasing treatment was carried out by washing the product at 45 ° C. for 2 minutes. After washing with water several times thereafter,
Using 0 g / l of activator (trade name: NC Rustol, manufactured by Okuno Chemical Industries Co., Ltd.) at 43 ° C. for 4 minutes, current density 5A
The electrolytic degreasing treatment was performed by washing under the condition of / dm ² . Subsequently, after washing with water several times, the acid activation treatment was performed by treating with 11% sulfuric acid at 25 ° C. for 1 minute, and then washing with water several times.

Next, the conductive substrate 101 which has been subjected to the above-mentioned treatment
On the other hand, a ruthenium plating solution (trade name: Ru-33, manufactured by NE Chemcat Co., Ltd.) having a ruthenium concentration of 8.5 g / l was used at 65 ° C., pH 2.1, and current density 1.
Metal R with a thickness of 0.45 μm was obtained by electroplating with a hook plating device under the condition of ² A / dm ² for 7 minutes.
A ruthenium layer 102 made of u was formed.

After washing with water several times, rinse with 11% ammonia water (50 ° C., 5 minutes)
After that, acid activation treatment was carried out by treating with 31% hydrochloric acid for 1 minute at 31 ° C.

Then, after washing with water several times, an alloy plating solution containing gold (Au) (gold (Au): 5 g / l, cobalt:
0.2 g / l; trade name: N80, manufactured by NE Chemcat Co., Ltd., 45 ° C., pH 4.
An alloy containing gold with a thickness of 0.11 μm (Au: 99.8% by mass) by electroplating with a hook plating device under conditions of 0 and a current density of 1.0 A / dm ² for 1.5 minutes.
The connector terminal shown in FIG. 1 was obtained by forming the surface metal layer 103 made of Co: 0.2% by mass .

The connector terminal thus obtained is
It has excellent contact resistance, insertability / extractability, heat resistance, and corrosion resistance, and therefore the connector having this connector terminal was extremely reliable.

Example 1 This example relates to a connector terminal in which an underlayer, a ruthenium layer, and a surface metal layer are formed in this order on a conductive substrate. Hereinafter, description will be made with reference to FIG.

First, the conductive substrate 201 has a thickness of 0.1.
mm tape-shaped phosphor bronze pressed into the shape of a connector terminal to form a continuous connector terminal
It was cut to a length of m. After the cutting, 55 g / l of activator (trade name: ESCREEN 30, manufactured by Okuno Chemical Industry Co., Ltd.)
Degreasing treatment was carried out by washing the product at 45 ° C. for 2 minutes. After washing with water several times thereafter,
Using 0 g / l of activator (trade name: NC Rustol, manufactured by Okuno Chemical Industries Co., Ltd.) at 43 ° C. for 4 minutes, current density 5A
The electrolytic degreasing treatment was performed by washing under the condition of / dm ² . Subsequently, after washing with water several times, the acid activation treatment was performed by treating with 11% sulfuric acid at 25 ° C. for 1 minute, and then washing with water several times.

Next, the conductive substrate 201 which has been subjected to the above-mentioned treatment
On the other hand, using a nickel plating solution (comprising 235 g / l nickel sulfate, 43 g / l nickel chloride, and 35 g / l boric acid) at 49 ° C., pH 3.8, and current density 4.2 A / dm ² . Undercoating was performed for 2 minutes by electroplating with a hook plating apparatus to form an underlayer 204 of Ni having a thickness of 1.9 μm.

Subsequently, after washing with water several times, a ruthenium plating solution (trade name: Ru-33, manufactured by NE Chemcat Co., Ltd.) having a ruthenium concentration of 8.5 g / l was formed on the underlayer 204. ) At 65 ° C., pH 2.1, and current density of 1.2 A / dm ² for 7 minutes by electroplating with a hook plating device to give a thickness of 0.44 μm.
Forming a ruthenium layer 202 made of Ru metal.

After washing with water several times, rinse with 11% ammonia water (50 ° C., 5 minutes)
After that, acid activation treatment was carried out by treating with 31% hydrochloric acid for 1 minute at 31 ° C.

Then, after washing with water several times, an alloy plating solution containing gold (Au) (gold (Au): 5 g / l, cobalt:
0.2 g / l; trade name: N80, manufactured by NE Chemcat Co., Ltd., 45 ° C., pH 4.
An alloy containing gold with a thickness of 0.12 μm (Au: 99.8% by mass) by electroplating with a hook plating device under conditions of 0 and a current density of 1.0 A / dm ² for 1.5 minutes.
By forming the surface metal layer 203 made of Co: 0.2% by mass, the connector terminal of the present invention shown in FIG. 2 was obtained.

The connector terminal thus obtained is
It has excellent contact resistance, insertability / extractability, heat resistance, and corrosion resistance, and therefore the connector having this connector terminal was extremely reliable.

Example 2 This example relates to a connector terminal in which a plurality of base layers, ruthenium layers, and surface metal layers are formed in this order on a conductive substrate. Hereinafter, description will be made with reference to FIG.

First, the conductive substrate 301 has a thickness of 0.1.
mm tape-shaped brass was pressed into the shape of a connector terminal, and a continuous connector terminal shape was cut into a length of 70 mm. After the cutting, a degreasing treatment was carried out by washing with 55 g / l of an activator (trade name: Escreen 30, manufactured by Okuno Chemical Industries Co., Ltd.) at 45 ° C. for 2 minutes. After washing with water several times, 90 g /
1 activator (trade name: NC Rustol, manufactured by Okuno Chemical Industries Co., Ltd.) at 43 ° C. for 4 minutes at a current density of 5 A / d
The electrolytic degreasing treatment was performed by washing under the condition of m ² . Subsequently, after washing with water several times, the acid activation treatment was performed by treating with 11% sulfuric acid at 25 ° C. for 1 minute, and then washing with water several times.

Next, the conductive substrate 301 which has been subjected to the above treatment
On the other hand, using a copper sulfate plating solution (comprising 105 g / l of copper sulfate, 155 g / l of sulfuric acid, 58 ppm of chlorine, and other additives) at 32 ° C., a current density of 4.2 A / dm ² , and air stirring. First made of Cu with a thickness of 1.5 μm by electroplating with a hook plating device.
Underlayer 304a was formed. Then, after washing with water several times, a nickel plating solution (made of 235 g / l nickel sulfate, 43 g / l nickel chloride, 35 g / l boric acid) was used on the first underlayer 304a. Second underlayer 30 made of Ni and having a thickness of 1.9 μm by electroplating for 2 minutes under the conditions of 49 ° C., pH 3.8, and current density of 4.2 A / dm ^2.
4b was formed.

Then, after washing with water several times,
On the second underlayer 304b, the ruthenium concentration is 8.5 g /
l ruthenium plating solution (trade name: Ru-33, N.
65 ° C, pH 2.
1, current density 1.2A / dm ²7 minutes under the conditions of
By electroplating with a plating device, a thickness of 0.
Form a Ruthenium layer 302 of 46 μm metal Ru
did.

After washing several times with water, rinsing with 11% ammonia water (50 ° C., 5 minutes)
After that, acid activation treatment was carried out by treating with 31% hydrochloric acid for 1 minute at 31 ° C.

Then, after washing with water several times, a rhodium plating solution (trade name: Rh22) having a rhodium concentration of 5.7 g / l was formed on the ruthenium layer 302 which had been subjected to the above treatment.
5, 56 by using Nchemcat Co., Ltd.
At a temperature of 1.0 ° C. and a current density of 1.0 A / dm ² , electroplating was performed for 1 minute by a hook plating apparatus to obtain a thickness of 0.
By forming the surface metal layer 303 of 11 μm rhodium Rh, the connector terminal of the present invention shown in FIG. 3 was obtained.

The connector terminal thus obtained is
It has excellent contact resistance, insertability / extractability, heat resistance, and corrosion resistance, and therefore the connector having this connector terminal was extremely reliable.

< Embodiment 3 > Similar to Embodiment 2 , this embodiment relates to a connector terminal in which a plurality of base layers, ruthenium layers, and surface metal layers are formed in this order on a conductive substrate. Below, FIG.
Will be described with reference to.

First, the conductive substrate 301 has a thickness of 0.1.
mm tape-shaped phosphor bronze pressed into the shape of a connector terminal to form a continuous connector terminal
It was cut to a length of m. After the cutting, 55 g / l of activator (trade name: ESCREEN 30, manufactured by Okuno Chemical Industry Co., Ltd.)
Degreasing treatment was carried out by washing the product at 45 ° C. for 2 minutes. After washing with water several times thereafter,
Using 0 g / l of activator (trade name: NC Rustol, manufactured by Okuno Chemical Industries Co., Ltd.) at 43 ° C. for 4 minutes, current density 5A
The electrolytic degreasing treatment was performed by washing under the condition of / dm ² . Subsequently, after washing with water several times, the acid activation treatment was performed by treating with 11% sulfuric acid at 25 ° C. for 1 minute, and then washing with water several times.

Next, the conductive substrate 301 which has been subjected to the above-mentioned treatment
On the other hand, using a nickel plating solution (comprising 235 g / l nickel sulfate, 43 g / l nickel chloride, and 35 g / l boric acid) at 49 ° C., pH 3.8, and current density 4.2 A / dm ² . The first underlayer 304a made of Ni and having a thickness of 1.8 μm was formed by electroplating for 2 minutes under a hooking plating apparatus. Then, after washing with water several times, a silver plating solution (consisting of 45 g / l silver and 105 g / l potassium cyanide) was used on the first underlayer 304a at 28 ° C. and pH 1
2.9, thickness 2.2 by electroplating with a hook plating device for 4 minutes under the condition of current density 1 A / dm ^2.
A second base layer 304b made of Ag having a thickness of μm was formed.

Then, after washing with water several times,
On the second underlayer 304b, the ruthenium concentration is 8.5 g /
l ruthenium plating solution (trade name: Ru-33, N.
65 ° C, pH 2.
1, current density 1.2A / dm ²7 minutes under the conditions of
By electroplating with a plating device, a thickness of 0.
Form a ruthenium layer 302 of 45 μm metal Ru
did.

After washing with water several times, rinse with 11% ammonia water (50 ° C., 5 minutes)
After that, acid activation treatment was carried out by treating with 31% hydrochloric acid for 1 minute at 31 ° C.

Then, after washing with water several times, an alloy plating solution containing gold (Au) (gold (Au): 3.5 g / l, nickel ( Ni): 0.2 g / l; Trade name: N205, N
E-Chem Cat Co., Ltd.) at 40 ° C., pH 0.
5. An alloy containing gold having a thickness of 0.1 μm (Au: 99.5 mass%, N by electroplating with a hook plating device for 0.5 minutes under the condition of current density 5.0 A / dm ²
By forming the surface metal layer 303 of i: 0.5% by mass, the connector terminal of the present invention shown in FIG. 3 was obtained.

The connector terminal thus obtained is
It has excellent contact resistance, insertability / extractability, heat resistance, and corrosion resistance, and therefore the connector having this connector terminal was extremely reliable.

Reference Example 2 This reference example relates to a connector terminal in which a ruthenium layer is formed on a conductive substrate and a plurality of surface metal layers are formed on the ruthenium layer. Hereinafter, description will be given with reference to FIG.

In Reference Example 1 , all steps were performed until the ruthenium layer was formed on the conductive substrate and the acid activation treatment was performed.
Similarly to the above, the ruthenium layer 40 is formed on the conductive substrate 401.
The connector terminal precursor which formed 2 was obtained.

Next, after washing with water several times, this connector terminal precursor was set in a hanging plating apparatus so that it was immersed in the plating bath in a state where it was laid horizontally, and a gold (Au) Alloy plating solution containing gold (gold (A
u): 5 g / l, cobalt: 0.2 g / l; trade name: N80, NE Chemcat Ltd.
Manufactured by K.K.) at 45 ° C., pH 4.0, current density 1.0 A /
An alloy containing gold having a thickness of 0.1 μm (Au: 99.90%) on the half of the ruthenium layer 402 by electroplating for 1.5 minutes under a condition of dm ^{2 by} a hook plating apparatus.
The first surface metal layer 403a composed of 8 mass% and Co: 0.2 mass% was formed.

Subsequently, the connector terminal precursor is turned upside down so that the ruthenium layer 402 on the side where the first surface metal layer 403a of the connector terminal precursor thus treated is not formed can be treated. And set it again in the hooking plating device, and tin (Sn) plating solution (55 g / l tin (Sn), 120 g / l organic acid (trade name: Metas AM, Yuken Industry Co., Ltd.), 30 cc / Using 1 liter of additive (trade name: SBS-R, manufactured by Yuken Industry Co., Ltd.), electroplating was performed by a hook plating apparatus for 3 minutes under the conditions of 40 ° C. and current density of 4 A / dm ² . Then, after washing three times with water, the surface was activated with 10 g / l of tertiary sodium phosphate at 75 ° C. for 1 minute. Next, the surface of the second surface metal layer made of tin (Sn) is formed on the other half of the ruthenium layer 402 by washing with pure water 5 times, draining with air, and drying at 70 ° C. for 5 minutes. Four
Connector end shown in FIG. 4 by forming 03b
Got a child When the thickness of the second surface metal layer 403b made of tin of this connector terminal was measured using a fluorescent X-ray film thickness measuring device (manufactured by Seiko Co., Ltd.), the thickness was 4.9 μm.

The connector terminal thus obtained is
It has excellent contact resistance, insertability / extractability, heat resistance, and corrosion resistance, and therefore the connector having this connector terminal was extremely reliable. Further, since the second surface metal layer 403b made of tin was formed, the solderability was excellent.

[0054] In <Comparative Example 1> Example 1, except that not form a ruthenium layer, the other is to produce a connector terminal in the same manner as in Example 1. Such a connector terminal has a structure in which a Ni layer and a surface metal layer are formed in this order on a conductive substrate, and corresponds to a conventional connector terminal.

<Hardness Test> Using each connector terminal obtained in Examples 1 to 3 and the connector terminal obtained in Comparative Example 1, a surface hardness tester (device name:
The surface hardness was measured from the surface of each surface metal layer under a measuring load of 10 g using a Vickus type surface hardness meter (Akasi Mfg. Co., Ltd.) . The results are shown in Table 1 below.

<Corrosion resistance test> The corrosion resistance of each of the connector terminals obtained in Examples 1 to 3 and the connector terminal obtained in Comparative Example 1 was measured. The measurement conditions were performed by spraying 5% saline and observing the degree of corrosion after 8 hours at 35 ° C. And, those that did not corrode were "○", those that were slightly corroded "△", those that were significantly corroded "X"
Evaluated as. The evaluation results are shown in Table 1 below.

[0057]

[Table 1]

As is clear from Table 1, the connector terminals of the respective examples have an excellent surface hardness as compared with the connector terminal of Comparative Example 1, so that peeling of the surface metal layer does not occur at all. In addition to the excellent insertability / extractability, the corrosion resistance test also showed excellent corrosion resistance. It should be noted that the surface hardness of each of the examples shows a variation in the value that the ruthenium layer alone exhibits a surface hardness of 700 to 850 HV, but the ruthenium layer is relatively thin, so that the conductive substrate existing as a lower layer of the layer is present. It is considered that the influence of the underlayer and the underlayer appeared.

The embodiments and examples disclosed this time must be considered as illustrative in all points and not restrictive. The scope of the present invention is shown not by the above description but by the claims, and is intended to include meanings equivalent to the claims and all modifications within the scope.

[0060]

EFFECTS OF THE INVENTION The connector terminal of the present invention has a ruthenium layer as a lower layer of the surface metal layer, so that the ruthenium layer and the surface metal layer interact with each other to have excellent surface hardness. , Effectively prevent wear and peeling of the surface metal layer,
Excellent mating and unmating properties are obtained while maintaining the excellent contact resistance of the surface metal layer, and pinholes are effectively prevented, resulting in dramatically improved qualities such as high hardness, heat resistance, and corrosion resistance. It is an improvement. Further, by forming two or more surface metal layers having different compositions from each other, it is possible to expand the range in which the connector terminals are used to a wider range. Further, by forming the underlayer as the lower layer of the ruthenium layer, peeling of the ruthenium layer can be effectively prevented regardless of the type of the conductive substrate. Further, if these underlayer, ruthenium layer and surface metal layer are formed by a plating method using either a barrel plating device, a hook plating device or a continuous plating device, these layers can be formed extremely efficiently. It will be possible. Therefore, the connector having the connector terminal of the present invention directly follows the unique advantages of such a connector terminal and has excellent contact resistance, insertability, heat resistance, and corrosion resistance, and is extremely reliable. It will be highly responsive. Therefore, the connector of the present invention can be widely used for electrical, electronic products, semiconductor products, automobile parts and the like.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a connector terminal in which a ruthenium layer and a surface metal layer are formed in this order on a conductive substrate.

FIG. 2 is a schematic cross-sectional view of a connector terminal in which a base layer, a ruthenium layer, and a surface metal layer are formed in this order on a conductive substrate.

FIG. 3 is a schematic cross-sectional view of a connector terminal in which a plurality of underlayers, ruthenium layers, and surface metal layers are formed in this order on a conductive substrate.

FIG. 4 is a schematic cross-sectional view of a connector terminal in which a ruthenium layer is formed on a conductive substrate and a plurality of surface metal layers are formed on the ruthenium layer.

[Explanation of symbols]

101, 201, 301, 401 conductive substrate, 10
2,202,302,402 ruthenium layer, 103,
203, 303 surface metal layer, 403a first surface metal layer, 403b second surface metal layer, 204 underlayer,
304a First underlayer, 304b Second underlayer.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-9-223771 (JP, A) JP-A-11-260178 (JP, A) JP-A-5-304229 (JP, A) JP-A-7- 220789 (JP, A) JP 5-174660 (JP, A) JP 11-126531 (JP, A) JP 2003-181976 (JP, A) JP 2003-171790 (JP, A) JP 2001-152385 (JP, A) JP-B-58-48969 (JP, B1) Patent 3442764 (JP, B2) (58) Fields investigated (Int.Cl. ⁷ , DB name) C25D 7/00 H01R 13/03

Claims (4)

(57) [Claims] 1. Ni, on the entire surface or a part of the conductive substrate ,
At least one kind of gold selected from the group consisting of Cu and Ag
Made of genus or alloys containing at least one of these metals
At least one underlayer is formed on the underlayer.
Of which a ruthenium layer over the entire surface or part is formed, Ag on the entire surface or part of the said ruthenium layer, Rh, Co,
At least one metal selected from the group consisting of Ni, In and Sn or Au, Ag, Rh, Co, Ni, In,
A connector terminal, wherein a surface metal layer made of an alloy containing at least one metal selected from the group consisting of Sn is formed. 2. The connector terminal according to claim 1, wherein two or more surface metal layers having different compositions are formed. 3. A base layer, a ruthenium layer and a surface metal layer are each a barrel plating apparatus, according to claim 1, characterized in that it is formed by a plating method using any of hooking plating apparatus or a continuous plating apparatus or Connector terminal described in 2 . 4. A connector having the connector terminal according to claim 1 .