JP5871206B2 - Manufacturing method of electrical contact material for connector - Google Patents

Description

The present invention relates to the production how the connector for electrical contact material.

  Generally, a copper (Cu) alloy is mainly used as an electrical contact material for a connector, but the Cu alloy has a contact resistance which is reduced by forming a non-conductor or an oxide film having a high electrical resistivity on the surface. This may cause an increase in reliability of the connection function.

  Therefore, a contact layer is usually formed by forming a metal plating layer having excellent corrosion resistance and being hardly oxidized on the surface of the Cu alloy, specifically, a noble metal plating layer such as gold (Au) plating or silver (Ag) plating. In order to suppress the increase in resistance, the reliability of the connection function is improved.

  However, since these noble metal platings are expensive, generally, tin (Sn) plating having a relatively high corrosion resistance while being inexpensive is used. However, since Sn plating is soft, it may be worn out to increase contact resistance. In addition, there is a drawback that the insertion force at the time of terminal insertion is increased.

As a technique to deal with such problems, a technique for forming a CuSn alloy layer on the outermost surface of the electrical contact material for connectors (for example, Patent Document 1), an Sn or Sn alloy layer is formed on the outermost surface, and a lower side thereof. A technique for forming an alloy layer containing an intermetallic compound mainly composed of Cu—Sn (for example, Patent Document 2), a technique for forming an Ag ₃ Sn alloy layer on a Sn-based plating layer (for example, Patent Document 3), etc. are proposed. Has been.

JP 2010-267418 A JP 2011-12350 A JP 2011-26677 A

  However, even with these technologies, it cannot be said that the above-mentioned problems have been sufficiently solved, and it is inexpensive and maintains a stable contact resistance over a long period of time, thereby ensuring electrical reliability and durability. There has been a demand for an electrical contact material for a connector that is excellent in performance and has a sufficiently small insertion force when a terminal is inserted.

As a result of intensive studies, the inventor has found that the above problems can be solved by the following technologies related to the present invention, and has completed the present invention. Below, the theory is bright for each technology.

The first technique related to the present invention is:
A metal layer forming step of forming a metal layer made of Ni, Sn, Al, Zn, Cu, In or an alloy thereof on the substrate;
An oxide layer removing step for removing the oxide layer formed after the metal layer forming step;
A conductive oxide layer forming step of oxidizing the surface of the metal layer from which the oxide layer has been removed to form a conductive oxide layer. It is a manufacturing method.

  While conducting various experiments and studies to solve the above problems, the present inventor forms a NiSn alloy layer or a CuSn alloy layer on a substrate, and removes the non-conductive oxide layer formed on the surface. After that, an oxidation treatment is performed to maintain a stable contact resistance for a long period of time, and it is excellent in electrical reliability and durability, and an electrical contact material for a connector having a sufficiently small insertion force at the time of inserting a terminal is obtained. It turns out that it is obtained.

That is, when a NiSn alloy layer is formed on a substrate, oxide layers of NiO and SnO, which are nonconductors, are formed on the surface of the alloy layer. When formed from different _NiO x (x ≠ 1) or a mixture of _NiO x (x ≠ 1) of _SnO y (y ≠ 1) and _SnO y (y ≠ 1) and the oxide layer is later nonconductor A conductive oxide layer of the compound is formed on the outermost surface.

In addition, when a CuSn alloy layer is formed on a base material, an oxide layer of CuO and SnO, which are nonconductors, is formed on the surface of the alloy layer. The oxide layer is removed and an oxidation treatment is performed. When formed from different _CuO x (x ≠ 1) or a mixture of _CuO x (x ≠ 1) of _SnO y (y ≠ 1) and _SnO y (y ≠ 1) and the oxide layer is later nonconductor A conductive oxide layer of the compound is formed on the outermost surface.

  Once such a conductive oxide is formed, oxidation does not proceed any more, so that the conductivity can be maintained over a long period of time, and a stable low contact resistance can be obtained. Since the NiSn alloy layer and the CuSn alloy layer are hard and excellent in wear resistance and have a low coefficient of friction, the insertion force at the time of terminal insertion can be made sufficiently small.

And as a result of further study, the present inventor is not limited to the NiSn alloy layer or the CuSn alloy layer, and the effect of forming the conductive oxide after the removal of the oxide layer as described above is not limited to Ni, It has been found that the same effect can be obtained even in a metal layer made of Sn, Al, Zn, Cu, In or an alloy thereof.

According to the present technology , since the conductive oxide layer is formed using extremely simple means in all of the formation of the metal layer, the removal of the oxide layer, and the oxidation treatment, the contact is stable while being inexpensive. It is possible to obtain an electrical contact material for a connector that has excellent electrical reliability and durability by maintaining resistance over a long period of time and has a sufficiently small insertion force when inserting a terminal. By using the connector, a connector having a stable contact resistance under a high temperature environment or vibration can be provided at low cost.

  In addition, as an oxidation treatment method in the “conductive oxide layer forming step”, an oxidation treatment with a liquid can be employed in addition to the oxidation treatment by heating. Natural oxidation may also be used.

The second technique related to the present invention is:
A metal layer forming step of forming a metal layer made of Ni, Sn, Al, Zn, Cu, In or an alloy thereof on the substrate;
An oxide layer removing step for removing the oxide layer formed after the metal layer forming step;
And a conductive hydroxide layer forming step of forming a conductive hydroxide layer by subjecting the surface of the metal layer from which the oxide layer has been removed to a hydroxylation treatment. It is a manufacturing method of an electrical contact material.

As a result of further experiments and studies by the inventor, the surface of the metal layer from which the non-conductive oxide layer has been removed is subjected to hydroxylation treatment using an anodic oxidation method or the like, whereby Ni (OH) ₂ , Cu ( It was found that conductive hydroxides such as (OH) ₂ and Sn (OH) ₂ were formed.

  Such a conductive hydroxide can maintain conductivity over a long period of time and can stably obtain a low contact resistance. The hydroxylation treatment is an industrially established means similar to the oxidation treatment described above. As a result, as described above, for a connector that is inexpensive but maintains stable contact resistance over a long period of time and has excellent electrical reliability and durability, and has a sufficiently small insertion force when inserting a terminal. An electrical contact material can be obtained, and by using such an electrical contact material for a connector, a connector having a stable contact resistance under a high temperature environment or vibration can be provided at low cost.

In addition, as a method of the hydroxylation treatment in the “conductive hydroxide layer forming step”, for example, an anodic oxidation method in an alkaline solution (for example, KOH, NH ₄ OH) can be exemplified.

The third technique related to the present invention is:
The metal layer forming step is a step of forming a NiSn alloy layer;
The conductive oxide layer forming step, forming a _NiO x (x ≠ 1) or a mixture of _NiO x (x ≠ 1) and _SnO y (y ≠ 1) are formed from the compounds of _SnO y (y ≠ 1) It is the process to perform, The manufacturing method of the electrical contact material for connectors as described in 1st technique characterized by the above-mentioned.

  As described above, as the metal layer, a metal layer made of Ni, Sn, Al, Zn, Cu, In or an alloy thereof can be adopted. Among these, the NiSn alloy is particularly hard and resistant. Since the wear resistance is excellent and the coefficient of friction is low, the insertion force at the time of inserting the terminal can be sufficiently reduced.

Then, by using this NiSn alloy and removing the surface oxide layer and performing an oxidation treatment, a mixture of NiO _x (x ≠ 1) and SnO _y (y ≠ 1) or A compound formed of NiO _x (x ≠ 1) and SnO _y (y ≠ 1) can be formed as a conductive oxide layer.

Each of NiO _x (x ≠ 1) and SnO _y (y ≠ 1) is a compound having excellent conductivity, but synergistically when both compounds are present as in the present invention. Since the number of carriers increases, the conductivity can be further improved.

The fourth technique related to the present invention is:
The metal layer forming step is a step of forming a CuSn alloy layer;
The conductive oxide layer forming step, forming a _CuO x (x ≠ 1) or a mixture of _CuO x (x ≠ 1) and _SnO y (y ≠ 1) are formed from the compounds of _SnO y (y ≠ 1) It is the process to perform, The manufacturing method of the electrical contact material for connectors as described in 1st technique characterized by the above-mentioned.

  As described above, a metal layer made of Ni, Sn, Al, Zn, Cu, In, or an alloy thereof can be adopted as the metal layer. Among these, the CuSn alloy is particularly hard and resistant. Since the wear resistance is excellent and the coefficient of friction is low, the insertion force at the time of inserting the terminal can be sufficiently reduced.

Then, by using a CuSn alloy layer and removing the surface oxide layer and performing an oxidation treatment, a mixture of CuO _x (x ≠ 1) and SnO _y (y ≠ 1) or A compound formed of CuO _x (x ≠ 1) and SnO _y (y ≠ 1) can be formed as a conductive oxide layer.

Each of CuO _x (x ≠ 1) and SnO _y (y ≠ 1) is a compound having excellent conductivity, but when both compounds exist as in the present technology , the carrier increases synergistically. Therefore, the conductivity can be further improved.

The fifth technique related to the present invention is:
The metal layer forming step is a step of forming a NiSn alloy layer;
Wherein the conductive hydroxide layer formation step is a step of forming a Ni _{(OH) 2} and Sn _(OH) a mixture of ₂ or Ni _{(OH) 2} and Sn _(OH) compound formed from ₂ It is a manufacturing method of the electrical contact material for connectors as described in the 2nd technique .

As described above, since the NiSn alloy is hard and excellent in wear resistance and has a low coefficient of friction, the insertion force at the time of inserting a terminal can be sufficiently reduced. Then, by using this NiSn alloy and removing the oxide layer on the surface and performing a hydroxylation treatment, a mixture of Ni (OH) ₂ and Sn (OH) ₂ or Ni (OH) is formed on the outermost surface of the alloy layer. ) The compound formed from ₂ and Sn (OH) ₂ can be formed as a conductive hydroxide layer, and stable contact resistance can be maintained over a long period of time.

The sixth technique related to the present invention is:
The metal layer forming step is a step of forming a CuSn alloy layer;
Wherein the conductive hydroxide layer formation step is a step of forming a Cu _{(OH) 2} and Sn _(OH) a mixture of ₂ or Cu _{(OH) 2} and Sn _(OH) compound formed from ₂ It is a manufacturing method of the electrical contact material for connectors as described in the 2nd technique .

As described above, since the CuSn alloy is hard and excellent in wear resistance and has a low coefficient of friction, the insertion force at the time of inserting a terminal can be sufficiently reduced. Then, using this CuSn alloy, the oxide layer on the surface is removed and subjected to a hydroxylation treatment, whereby a mixture of Cu (OH) ₂ and Sn (OH) ₂ or Cu is formed on the outermost surface of the alloy layer. A compound formed from (OH) ₂ and Sn (OH) ₂ can be formed as a conductive hydroxide layer, and stable contact resistance can be maintained over a long period of time.

The seventh technique related to the present invention is:
The method for producing an electrical contact material for a connector according to the third technique or the fifth technique , wherein the step of forming the NiSn alloy layer is a step of forming a NiSn alloy layer using an alloy plating bath. It is.

  By using the alloy plating bath, the NiSn alloy layer can be easily formed.

The eighth technique related to the present invention is:
The method for producing an electrical contact material for a connector according to the fourth technique or the sixth technique , wherein the step of forming the CuSn alloy layer is a step of forming a CuSn alloy layer using an alloy plating bath. It is.

  By using an alloy plating bath, a CuSn alloy layer can be easily formed.

The ninth technique related to the present invention is:
The third or fifth technique is characterized in that the step of forming the NiSn alloy layer is a step of forming a NiSn alloy layer by stacking one or more Ni layers and Sn layers and then heat-treating them. It is a manufacturing method of the electrical contact material for connectors as described in above.

  A NiSn alloy layer having a desired ratio can be easily formed by stacking at least one Ni layer and one Sn layer and then heat-treating to form a NiSn alloy layer.

The tenth technique related to the present invention is:
The fourth or sixth technique is characterized in that the step of forming the CuSn alloy layer is a step of forming a CuSn alloy layer by performing heat treatment after laminating one or more Cu layers and Sn layers. It is a manufacturing method of the electrical contact material for connectors as described in above.

  A CuSn alloy layer having a desired ratio can be easily formed by stacking one or more Cu layers and Sn layers and then heat-treating to form a CuSn alloy layer.

The eleventh technology related to the present invention is:
The method for producing an electrical contact material for a connector according to the ninth technique , wherein the Ni layer and the Sn layer are formed by electroplating.

  By forming the Ni layer and the Sn layer by electroplating, it is possible to form the Ni layer and the Sn layer having high purity at a relatively low cost.

The twelfth technique related to the present invention is:
The method for producing an electrical contact material for a connector according to the tenth technique , wherein the Cu layer and the Sn layer are formed by electroplating.

  By forming the Cu layer and the Sn layer by electroplating, it is possible to form the Cu layer and the Sn layer having high purity at a relatively low cost.

The thirteenth technique related to the present invention is:
The method for producing an electrical contact material for a connector according to the ninth technique , wherein the Ni layer and the Sn layer are formed by vapor deposition.

  By forming the Ni layer and the Sn layer by a vapor deposition method, it is possible to form the Ni layer and the Sn layer with excellent film thickness control.

The fourteenth technology related to the present invention is:
The method for producing an electrical contact material for a connector according to the tenth technique , wherein the Cu layer and the Sn layer are formed by vapor deposition.

  By forming the Cu layer and the Sn layer by the vapor deposition method, it is possible to form the Cu layer and the Sn layer with excellent film thickness control.

The fifteenth technology related to the present invention is:
Prior to the formation of the NiSn alloy layer or a CuSn alloy layer, a connector for electrical contact material according to any one of the second technique to fourteenth technology characterized by providing a Ni layer on said substrate It is a manufacturing method.

  By providing a Ni layer on the base material as a diffusion barrier layer to prevent plating swelling and peeling, the adhesion between the NiSn alloy layer or CuSn alloy layer and the base metal can be improved, and workability is improved. Can also be improved. As a specific means for providing the Ni layer, for example, a plating method can be cited.

The sixteenth technology related to the present invention is:
Any one of the first to fifteenth techniques is characterized in that the oxide layer removing step is a step of removing the oxide layer by acid or alkali etching, electrolytic etching, dry etching or mechanical polishing. a method for producing a connector for the electrical contact material according to One.

  Etching with acid or alkali, electrolytic etching, dry etching, and mechanical polishing are already established techniques, and the oxide layer can be easily removed using existing equipment.

The seventeenth technology related to the present invention is:
The oxide layer removing step, the second technique to the connector for electrical contact material according to any one of the fifteenth technology characterized by the step of removing the oxide layer by Sn plating stripping solution It is a manufacturing method.

  When Sn is present on the outermost surface, SnO, which is a nonconductor, is generated, but the oxide layer can be easily removed by using a Sn plating stripper.

The eighteenth technique related to the present invention is:
It said substrate, Cu, Al, a method of manufacturing a Fe or the first technique to a connector for electrical contact material according to any one of the seventeenth technical, characterized in that an alloy thereof.

  Cu, Al, Fe or their alloys are preferable as a base material for an electrical contact material for connectors because they are excellent in conductivity and moldability and also in spring properties.

The nineteenth technology related to the present invention is:
On the base material, a metal layer made of Ni, Sn, Al, Zn, Cu, In or an alloy thereof is formed,
An electrical contact material for a connector, wherein a conductive oxide layer or a conductive hydroxide layer is formed on the metal layer.

  As described above, the conductive oxide layer and the conductive hydroxide layer are formed on the metal layer made of Ni, Sn, Al, Zn, Cu, In, or an alloy thereof. Thus, conductivity can be maintained, and a low contact resistance can be stably obtained. Moreover, the insertion force at the time of terminal insertion can be made sufficiently small.

The twentieth technique related to the present invention is:
The metal layer is a NiSn alloy layer;
Said conductive oxide layer is an _NiO x (x ≠ 1) or a mixture of _NiO x (x ≠ 1) and compound formed from _SnO y (y ≠ 1) of _SnO y (y ≠ 1) The electrical contact material for a connector according to the nineteenth technology , which is characterized.

As described above, since the NiSn alloy layer is hard and excellent in wear resistance and has a low coefficient of friction, the insertion force at the time of terminal insertion can be made sufficiently small. Then, the mixture or _NiO x (x ≠ 1) and _SnO y (y ≠ 1) are formed from the compounds of _NiO x, which is formed on the NiSn alloy layer (x ≠ 1) and _SnO y (y ≠ 1) A conductive oxide is preferable because it has a large effect of improving conductivity.

The twenty-first technique related to the present invention is:
The metal layer is a CuSn alloy layer;
Said conductive oxide layer is a mixture or _CuO x (x ≠ 1) and compound formed from _SnO y (y ≠ 1) of _CuO x (x ≠ 1) and _SnO y (y ≠ 1) The electrical contact material for a connector according to the nineteenth technology , which is characterized.

As described above, since the CuSn alloy layer is hard and excellent in wear resistance and has a low coefficient of friction, the insertion force at the time of inserting a terminal can be sufficiently reduced. Then, the mixture or _CuO x (x ≠ 1) and _SnO y (y ≠ 1) are formed from the compounds of _CuO x formed on the CuSn alloy layer (x ≠ 1) and _SnO y (y ≠ 1) A conductive oxide is preferable because it has a large effect of improving conductivity.

The twenty-second technique related to the present invention is:
The metal layer is a NiSn alloy layer;
19 technique the conductive hydroxide layer, characterized in that it is a Ni _{(OH) 2} and Sn _(OH) a mixture of ₂ or Ni _{(OH) 2} and Sn _(OH) compound formed from ₂ It is an electrical contact material for connectors as described in above.

As described above, since the NiSn alloy layer is hard and excellent in wear resistance and has a low coefficient of friction, the insertion force at the time of terminal insertion can be made sufficiently small. Then, conductive hydroxide Ni _{(OH) 2} and Sn _(OH) a mixture of ₂ or Ni _{(OH) 2} and Sn _(OH) compound formed from ₂ formed on the NiSn alloy layer is electrically conductive It is preferable because the effect of improving the property is large.

The twenty-third technique related to the present invention is:
The metal layer is a CuSn alloy layer;
19 technique the conductive hydroxide layer, characterized in that a Cu _{(OH) 2} and Sn _(OH) a mixture of ₂ or Cu _{(OH) 2} and Sn _(OH) compound formed from ₂ It is an electrical contact material for connectors as described in above.

As described above, since the CuSn alloy layer is hard and excellent in wear resistance and has a low coefficient of friction, the insertion force at the time of inserting a terminal can be sufficiently reduced. The conductive hydroxide of the compound formed from a mixture of Cu (OH) ₂ and Sn (OH) ₂ or Ni (OH) ₂ and Sn (OH) ₂ formed on the CuSn alloy layer is conductive. It is preferable because the effect of improving the property is large.

The 24th technology related to the present invention is:
Between the NiSn alloy layer or a CuSn alloy layer and the base material, a connector for electrical contacts according to any one of the first 23 technical to no twentieth technology characterized the Ni layer is provided Material.

  As described above, it is preferable that the Ni layer as the diffusion barrier layer is provided on the substrate because adhesion between the NiSn alloy layer or CuSn alloy layer and the base metal is improved and workability is improved.

The twenty-fifth technology related to the present invention is:
A connector for electrical contacts, characterized in that it is formed with a connector for electrical contact material according to to any one of the 24th technical no nineteenth technical.

  By using these electrical contact materials for connectors, it is inexpensive but maintains stable contact resistance over a long period of time, providing excellent electrical reliability and durability, and sufficient insertion force when inserting terminals. Small connector electrical contacts can be provided. By using such an electrical contact material for a connector, it is possible to provide a connector having a stable contact resistance under a high temperature environment or vibration.

  The present invention has been made on the basis of the above-described technologies, and the invention according to claim 1
  A metal layer forming step of forming a metal layer made of Ni, Sn, Al, Zn, Cu, In or an alloy thereof on the substrate;
  An oxide layer removing step of removing the non-conductive oxide layer formed after the metal layer forming step;
  A conductive oxide layer forming step of forming a conductive oxide layer by oxidizing the surface of the metal layer from which the oxide layer has been removed;
Have
  The method for producing an electrical contact material for a connector, wherein the oxide layer removing step is a step of removing the oxide layer by acid or alkali etching, electrolytic etching, dry etching or mechanical polishing.

  The invention described in claim 2
  A metal layer forming step of forming a metal layer made of Ni, Sn, Al, Zn, Cu, In or an alloy thereof on the substrate;
  An oxide layer removing step of removing the non-conductive oxide layer formed after the metal layer forming step;
  A conductive hydroxide layer forming step of forming a conductive hydroxide layer by hydroxylating the surface of the metal layer from which the oxide layer has been removed;
Have
  The method for producing an electrical contact material for a connector, wherein the oxide layer removing step is a step of removing the oxide layer by acid or alkali etching, electrolytic etching, dry etching or mechanical polishing.

  The invention according to claim 3
  The metal layer forming step is a step of forming a NiSn alloy layer;
  The conductive oxide layer forming step is performed using NiO. _x (X ≠ 1) and SnO _y Mixture of (y ≠ 1) or NiO _x (X ≠ 1) and SnO _y It is a step of forming a compound formed from (y ≠ 1)
It is a manufacturing method of the electrical contact material for connectors of Claim 1 characterized by the above-mentioned.

  The invention according to claim 4
  The metal layer forming step is a step of forming a CuSn alloy layer;
  The conductive oxide layer forming step includes CuO. _x (X ≠ 1) and SnO _y (Y ≠ 1) mixture or CuO _x (X ≠ 1) and SnO _y It is a step of forming a compound formed from (y ≠ 1)
It is a manufacturing method of the electrical contact material for connectors of Claim 1 characterized by the above-mentioned.

  The invention described in claim 5
  The metal layer forming step is a step of forming a NiSn alloy layer;
  The conductive hydroxide layer forming step includes Ni (OH) ₂ And Sn (OH) ₂ A mixture of or Ni (OH) ₂ And Sn (OH) ₂ It is a process of forming a compound formed more
The method for producing an electrical contact material for a connector according to claim 2.

  The invention described in claim 6
  The metal layer forming step is a step of forming a CuSn alloy layer;
  The conductive hydroxide layer forming step is Cu (OH) ₂ And Sn (OH) ₂ Or Cu (OH) ₂ And Sn (OH) ₂ It is a process of forming a compound formed more
The method for producing an electrical contact material for a connector according to claim 2.

  The invention described in claim 7
  The method for producing an electrical contact material for a connector according to claim 3 or 5, wherein the step of forming the NiSn alloy layer is a step of forming the NiSn alloy layer using an alloy plating bath. .

  The invention according to claim 8 provides:
  The method for producing an electrical contact material for a connector according to claim 4 or 6, wherein the step of forming the CuSn alloy layer is a step of forming a CuSn alloy layer using an alloy plating bath. .

  The invention according to claim 9 is:
  6. The step of forming the NiSn alloy layer is a step of forming a NiSn alloy layer by heat-treating after laminating one or more Ni layers and Sn layers, respectively. It is a manufacturing method of the electrical contact material for connectors.

  The invention according to claim 10 is:
  7. The step of forming the CuSn alloy layer is a step of forming a CuSn alloy layer by performing heat treatment after laminating one or more Cu layers and Sn layers, respectively. It is a manufacturing method of the electrical contact material for connectors.

  The invention according to claim 11
  The method for producing an electrical contact material for a connector according to claim 9, wherein the Ni layer and the Sn layer are formed by electroplating.

  The invention according to claim 12
  The method for producing an electrical contact material for a connector according to claim 10, wherein the Cu layer and the Sn layer are formed by electroplating.

  The invention according to claim 13
  The method for producing an electrical contact material for a connector according to claim 9, wherein the Ni layer and the Sn layer are formed by vapor deposition.

  The invention according to claim 14
  The method for producing an electrical contact material for a connector according to claim 10, wherein the Cu layer and the Sn layer are formed by vapor deposition.

  The invention according to claim 15 is:
  15. The electrical contact material for a connector according to claim 2, wherein a Ni layer is provided on the substrate prior to the formation of the NiSn alloy layer or the CuSn alloy layer. Is the method.

  The invention described in claim 16
  The method for producing an electrical contact material for a connector according to any one of claims 2 to 15, wherein the oxide layer removing step is a step of removing the oxide layer with a Sn plating stripping solution. It is.

  The invention described in claim 17
  The method of manufacturing an electrical contact material for a connector according to any one of claims 1 to 16, wherein the base material is Cu, Al, Fe, or an alloy thereof.

  According to the present invention, an electrical contact material for a connector that is inexpensive and maintains a stable contact resistance over a long period of time, has excellent electrical reliability and durability, and has a sufficiently small insertion force when a terminal is inserted. By using such an electrical contact material for a connector, it is possible to provide a connector having a stable contact resistance under a high temperature environment or vibration.

It is sectional drawing which shows typically the structure of the electrical contact material for connectors which concerns on one embodiment of this invention. It is a flow explaining the manufacturing method of the electrical contact material for connectors which concerns on one embodiment of this invention. It is a figure explaining the procedure which forms the NiSn alloy layer of Example 1. FIG. It is a figure which shows the measurement result of the contact resistance of the electrical contact material for connectors before and after the oxide layer removal of Example 1. It is a figure which shows the measurement result of the contact resistance of the electrical contact material for connectors before and behind the heat processing of Example 1. FIG. It is a figure which shows the structure and contact resistance of the electrical contact material for connectors in each process of Example 1. FIG. It is sectional drawing which shows typically the structure of the electrical contact material for connectors of Example 2. FIG. It is a figure which shows the measurement result of the contact resistance of the electrical contact material for connectors before and after the oxide layer removal of Example 2, and after heat processing. It is a flow explaining the manufacturing method of the electrical contact material for connectors which concerns on other embodiment of this invention. It is a figure explaining the procedure which forms the CuSn alloy layer of Example 3. FIG. It is a figure which shows the measurement result of the contact resistance of the electrical contact material for connectors before and behind the oxide layer removal of Example 3. It is a figure which shows the measurement result of the contact resistance of the electrical contact material for connectors before and behind the heat processing of Example 3. FIG.

  Hereinafter, the present invention will be described with reference to the drawings based on embodiments.

(First embodiment)
In the first embodiment, a NiSn alloy layer is formed as an alloy layer.

1. Configuration of Electrical Contact Material for Connector First, the configuration of the electrical contact material for connector will be described. FIG. 1 is a cross-sectional view schematically showing a configuration of a connector electrical contact material according to the present embodiment. In FIG. 1, 1 is a base material, 2 is a diffusion barrier layer, 3 is a metal layer, 4 is a conductive oxide layer or a conductive hydroxide layer.

(1) Base Material The base material 1 is preferably a material that is excellent in conductivity and moldability and excellent in spring properties, and specifically, Cu, Al, Fe, or alloys thereof are preferably used. As thickness, about 0.2-2 mm is preferable. A cylindrical terminal may be used.

  In order to prevent plating swelling and peeling, a diffusion barrier layer 2 may be provided on the surface of the substrate 1 as necessary. As the diffusion barrier layer 2, for example, a Ni layer is preferably used, and the thickness is preferably about 0.5 to 5 μm.

(2) Metal layer The metal layer 3 is a metal layer made of Ni, Sn, Al, Zn, Cu, In, or an alloy thereof. In the case of an alloy layer, the ratio of the metal element is not particularly limited as long as it is an alloy that can form a conductive oxide layer by oxidizing after removing the oxide layer. For example, the NiSn alloy layer In this case, a Ni ₃ Sn ₄ alloy layer or a NiSn ₃ alloy layer is preferably used. As thickness, about 0.1-5 micrometers is preferable.

(3) Conductive oxide layer or conductive hydroxide layer (3-1) Conductive oxide layer The conductive oxide layer 4 is an oxide of the metal layer 3, for example, NiO _x (x ≠ 1 ) (Specifically, for example, NiO _{1.5, that} is, Ni ₂ O ₃ ), SnO _y (y ≠ 1) (specifically, for example, SnO ₂ ), ZnO, CuO ₂ , CuAlO ₂ , In ₂ O ₃ etc. can be mentioned. Specific examples of the mixture of NiO _x (x ≠ 1) and SnO _y (y ≠ 1) include NiSnO ₃ and Ni ₂ (SnO ₃ ) ₃ . In addition, a compound formed of NiO _x (x ≠ 1) and SnO _y (y ≠ 1) can also be used. The thickness is preferably about 1 to 200 nm, more preferably about 1 to 50 nm.

(3-2) Conductive hydroxide layer The conductive hydroxide layer 4 is a hydroxide of the metal layer 3, such as Ni (OH) ₂ or Sn (OH) ₂ , or Ni (OH ) ₂ and Sn _(OH) as a mixture or Ni _(OH) compound formed from ₂ and Sn _{(OH) 2} and _2, for example, _{Ni [Sn (OH) 6]} , Ni 2 [Sn (OH) 6] 3 And so on. The thickness is preferably about 1 to 200 nm, more preferably about 1 to 50 nm.

2. Next, a method for manufacturing a connector electrical contact material will be described based on the flow shown in FIG. 2 by taking the case where the metal layer 3 is a NiSn alloy layer as an example.

  As shown in FIG. 2, the connector electrical contact material according to the present embodiment is formed on the base material 1 provided with the diffusion barrier layer 2 by forming the NiSn mixed metal 3, removing the SnO or NiO oxide layer, It is manufactured by forming the conductive oxide layer or the conductive hydroxide layer 4.

(1) Formation process of NiSn alloy layer The NiSn alloy layer 3 is formed by appropriately selecting and employing any one of the following methods (a) to (d).

(A) NiSn alloy is directly electroplated with an alloy plating bath.

(B) Ni plating and Sn plating are performed by electroplating, and after the Ni layer and the Sn layer are laminated, a NiSn alloy layer is formed by heat treatment. At this time, either the Ni layer or the Sn layer may be formed first.

(C) After a Ni layer and a Sn layer are stacked by vapor deposition, a NiSn alloy layer is formed by heat treatment. At this time, either the Ni layer or the Sn layer may be formed first.

(D) A NiSn alloy layer is directly formed by vapor deposition.

(2) Step of removing oxide layer Next, NiO, SnO, etc. generated on the surface of the NiSn alloy layer 3 by wet etching with acid or alkali, electrolytic etching using an electrolytic solution, dry etching or mechanical polishing are removed. The oxide layer (oxide film) is removed. Further, when Sn remains on the surface, SnO may be generated. Therefore, this Sn is removed using a Sn plating stripping solution.

(3) Formation Step of Conductive Oxide Layer or Conductive Hydroxide Layer Next, the surface of the NiSn alloy layer 3 is obtained by oxidizing or hydroxylating the surface of the NiSn alloy layer 3 from which the oxide film has been removed. A conductive oxide layer or a conductive hydroxide layer 4 is formed on the substrate. As specific oxidation treatment methods, any of oxidation treatment by heating, oxidation treatment by liquid, and oxidation treatment by natural oxidation can be adopted. Specific examples of the hydroxylation method include a method of anodizing in an aqueous KOH solution, an anodizing treatment in an aqueous solution of NiSO ₄ and NH ₄ OH, and the like.

(Second Embodiment)
In the second embodiment, a CuSn alloy layer is formed as the alloy layer.

1. Configuration of Electrical Contact Material for Connector As the electrical contact material for connector in the present embodiment, the electrical contact material for connector having the configuration shown in FIG. 1 can be used as in the first embodiment.

(1) Substrate As described above, the substrate 1 is preferably a material that is excellent in conductivity and moldability and excellent in spring properties, and specifically, Cu, Al, Fe, or an alloy thereof is used. Preferably used. As thickness, about 0.2-2 mm is preferable. A cylindrical terminal may be used.

  In order to prevent plating swelling and peeling, a diffusion barrier layer 2 may be provided on the surface of the substrate 1 as necessary. As the diffusion barrier layer 2, for example, a Ni layer is preferably used, and the thickness is preferably about 0.5 to 5 μm.

(2) Metal layer The metal layer 3 in the present embodiment is a CuSn alloy layer, and an alloy that can form a conductive oxide layer by oxidizing after removing the oxide layer in the same manner as described above. If so, the ratio of the metal element is not particularly limited, but a Cu ₆ Sn ₅ alloy layer or the like is preferably used. As thickness, about 0.1-5 micrometers is preferable.

(3) Conductive oxide layer or conductive hydroxide layer (3-1) Conductive oxide layer The conductive oxide layer 4 is an oxide of the metal layer 3, for example, CuO _x (x ≠ 1 ) (Specifically, for example, Cu ₂ O), SnO _y (y ≠ 1) (specifically, for example, SnO ₂ ), ZnO, CuO ₂ , CuAlO ₂ , In ₂ O _{3 and the} like. it can. A compound formed from CuO _x (x ≠ 1) and SnO _y (y ≠ 1) can also be used. The thickness is preferably about 1 to 200 nm, more preferably about 1 to 50 nm.

(3-2) Conductive hydroxide layer The conductive hydroxide layer 4 is a hydroxide of the metal layer 3, such as Cu (OH) ₂ or Sn (OH) ₂ , and Cu (OH). ) ₂ and Sn (OH) ₂ and compounds formed from Cu (OH) ₂ and Sn (OH) ₂ . The thickness is preferably about 1 to 200 nm, more preferably about 1 to 50 nm.

2. Next, the manufacturing method of the electrical contact material for a connector when the metal layer 3 is a CuSn alloy layer will be described based on the flow shown in FIG.

  As shown in FIG. 9, the electrical contact material for a connector according to the present embodiment is formed on the base material 1 on which the diffusion barrier layer 2 is formed, by forming a CuSn alloy 3, removing a SnO or CuO oxide layer, It is manufactured by forming the conductive oxide layer or the conductive hydroxide layer 4.

(1) Forming process of CuSn alloy layer The CuSn alloy layer 3 is formed by appropriately selecting and adopting any of the methods shown in the following (A) to (D).

(A) The CuSn alloy is electroplated directly in an alloy plating bath.

(B) Cu plating and Sn plating are performed by electroplating, a Cu layer and a Sn layer are laminated, and then a heat treatment is performed to form a CuSn alloy layer. At this time, either the Cu layer or the Sn layer may be formed first.

(C) After the Cu layer and the Sn layer are stacked by vapor deposition, a CuSn alloy layer is formed by heat treatment. At this time, either the Cu layer or the Sn layer may be formed first.

(D) A CuSn alloy layer is directly formed by vapor deposition.

(2) Oxide layer removal step Next, CuO, SnO, etc. generated on the surface of the CuSn alloy layer 3 by wet etching with acid or alkali, electrolytic etching using an electrolytic solution, dry etching, or mechanical polishing. The oxide layer (oxide film) is removed. Further, when Sn remains on the surface, SnO may be generated. Therefore, this Sn is removed using a Sn plating stripping solution.

(3) Formation Step of Conductive Oxide Layer or Conductive Hydroxide Layer Next, the surface of the CuSn alloy layer 3 is obtained by oxidizing or oxidizing the surface of the CuSn alloy layer 3 from which the oxide film has been removed. A conductive oxide layer or a conductive hydroxide layer 4 is formed on the substrate. As specific oxidation treatment methods, any of oxidation treatment by heating, oxidation treatment by liquid, and oxidation treatment by natural oxidation can be adopted. Specific examples of the hydroxylation method include a method of anodizing in an aqueous KOH solution, an anodizing treatment in an aqueous solution of NiSO ₄ and NH ₄ OH, and the like.

Example 1
In this example, a conductive oxide layer was formed on a NiSn alloy layer, and an electrical contact material for a connector was produced according to the following steps.

1. Formation of NiSn Alloy Layer A NiSn alloy layer was formed on a brass substrate according to the procedure shown in FIG.

(1) Formation of Ni layer First, electroplating was performed on a brass base material under the following conditions to form a Ni layer having a thickness of 2 μm (see FIG. 3A).

(B) Structure of plating bath Nickel sulfate 265g / L
Nickel chloride 45g / L
Boric acid 40g / L
Brightener (b) Current density 0.5 A / dm ²
(C) Temperature 50 ° C

(2) Formation of Sn layer Next, electroplating was performed on the Ni layer under the following conditions to form a Sn layer having a thickness of 6.6 μm (see FIG. 3A).

(B) Structure of plating bath Stannous sulfate 40 g / L
Sulfuric acid 100g / L
Brightener (b) Current density 0.5 A / dm ²
(C) Temperature 20 ° C

(3) Heat treatment Next, heat treatment was performed at 200 ° C. for 216 hr (9 days) to form a NiSn alloy layer as shown in FIG.

2. Composition analysis of NiSn alloy layer (1) Analysis method Composition analysis of the NiSn alloy layer was performed by X-ray diffraction and EDX. The composition of the surface was analyzed by XPS.

(2) Analysis result It was found by composition analysis that Ni ₃ Sn ₄ was formed in the NiSn alloy layer. It was also found that SnO was mainly formed as an oxide layer on the surface, and Ni was present as a metal bond.

3. Removal of oxide layer Next, the oxide layer on the surface of the NiSn alloy layer was removed by dry etching.

4). Contact resistance measurement (confirmation of removal of oxide layer)
The contact resistance before and after removal of the oxide layer was measured.

(1) Measurement method Using a gold plating emboss with a radius of 3 mm, the contact resistance at each load when the load was changed and contacted with the gold plating emboss was measured using a four-terminal method (FR test) (N = 3). The energizing current was 10 mA and the maximum load was 40N.

(2) Measurement results The measurement results are shown in FIG. As shown in FIG. 4, the sample after the removal of the oxide layer (etching treatment 01, 02, 03) has a higher contact resistance than the sample before the removal of the oxide layer (treatment 01, 02, 03). It was confirmed that the oxide layer which is a nonconductor was sufficiently removed.

5. Formation of Conductive Oxide Layer Next, heat treatment was performed at 160 ° C. for 120 hours to form a conductive oxide layer on the surface.

6). Composition analysis of conductive oxide layer (1) Analytical method Composition analysis of the surface after heat treatment was performed by XPS.

(2) Analysis result By composition analysis, it was found that Ni, Sn, and O were detected on the outermost surface, and an oxide having a constant Ni and Sn ratio was formed. Ni exists as an oxide NiO _x (specifically, Ni ₂ O ₃ ) or a metal bond, and Sn mainly exists as an oxide SnO _x (specifically, SnO ₂ ) or a metal bond. I found out that

7). Measurement of contact resistance The contact resistance before and after the heat treatment was measured in the same manner as described above (N = 3). The measurement results are shown in FIG. As shown in FIG. 5, the change in contact resistance is small before and after the heat treatment. This is because a conductive oxide layer is formed on the surface of the NiSn alloy layer.

  FIG. 6 shows the cross-sectional configuration (a) in each step and the contact resistance (b) when measured with a load of 10N. In FIG. 6, an Au plated product is also shown for reference.

  As shown in FIG. 6B, in this example, the contact resistance, which was 1.1 mΩ before the formation of the NiSn alloy layer, is greatly increased to 34.0 mΩ after the formation of the NiSn alloy layer. This is because SnO, which is a nonconductor, is formed on the surface of the NiSn alloy layer.

  And by removing SnO by dry etching, the contact resistance is greatly reduced from 34.0 mΩ to 2.3 mΩ.

And this lowered contact resistance does not increase to 1.7 mΩ even after the heat treatment. This is the surface of the NiSn alloy layer, conduction _NiO x (x ≠ 1) or a mixture of _NiO x (x ≠ 1) and _SnO y (y ≠ 1) are formed from the compounds of _SnO y (y ≠ 1) This is because the conductive oxide layer is formed.

  Although this contact resistance value is slightly higher than the contact resistance value in gold plating, it is inferior as the resistance value as a connector contact, and as an inexpensive alternative material to conventional terminals that are expensive gold plating It shows that it can be adopted. By using such an electrical contact material for a connector, it is possible to obtain a highly durable connector having a sufficiently small contact resistance and stable.

(Example 2)
In this example, an electrical contact material for a connector was produced according to the following steps.

1. Formation of NiSn Alloy Layer Using a brass substrate (Hull cell substrate) on which a Ni layer having a thickness of 5 μm was formed as a base material, NiSn alloy plating was performed under the following conditions to form a NiSn alloy layer having a thickness of 0.3 μm ( (See FIG. 7).

(A) Structure of plating bath Tin chloride (SnCl ₂ .2H ₂ O) 0.125 mol / L
Nickel chloride _{(NiCl 2 · 6H 2 O)} 0.125mol / L
K ₄ P ₂ O ₇ 0.5 mol / L
Glycine 0.25 mol / L
(B) Current density 0.5 A / dm ²
(C) Temperature 50 ° C

2. Removal of oxide layer Next, the oxide layer on the surface of the NiSn alloy layer was removed by immersing in hydrochloric acid for 5 minutes.

3. Formation of Conductive Oxide Layer Next, heat treatment was performed at 160 ° C. for 120 hours to form a conductive oxide layer on the surface.

4). Measurement of Contact Resistance Before and after the removal of the oxide layer and the formation of the conductive oxide layer, the contact resistance was measured in the same manner as described above. The results are shown in FIG.

  From the results shown in FIG. 8, the contact resistance is high only by forming the NiSn metal layer, and the material unsuitable as the electrical contact material for the connector decreases the contact resistance by removing the surface oxide by hydrochloric acid treatment, Further, even when heat treatment is performed, the conductive oxide layer is formed, so that the resistance value does not increase, and it can be seen that a suitable electrical contact material for connectors is obtained.

(Example 3)
In this example, a conductive oxide layer was formed on a CuSn alloy layer, and an electrical contact material for a connector was produced according to the following steps.

1. Formation of CuSn Alloy Layer A CuSn alloy layer was formed on a brass substrate according to the procedure shown in FIG.

(1) Formation of Ni layer First, electroplating was performed on a brass base material under the following conditions to form a Ni layer having a thickness of 2 μm (see FIG. 10A).

(B) Structure of plating bath Nickel sulfate 265g / L
Nickel chloride 45g / L
Boric acid 40g / L
Brightener (b) Current density 0.5 A / dm ²
(C) Temperature 50 ° C

(2) Formation of Cu Layer Next, electroplating was performed on the Ni layer under the following conditions to form a Cu layer having a thickness of 1 μm (see FIG. 10A).

(I) Structure of plating bath Copper sulfate 180g / L
Sulfuric acid 80g / L
Chloride ion 40mL / L
(B) Current density 1 A / dm ²
(C) Temperature 20 ° C

(3) Formation of Sn layer Next, electroplating was performed on the Cu layer under the following conditions to form a Sn layer having a thickness of 2 μm (see FIG. 10A).

(B) Structure of plating bath Stannous sulfate 40 g / L
Sulfuric acid 100g / L
Brightener (b) Current density 0.5 A / dm ²
(C) Temperature 20 ° C

(3) Heat treatment Next, heat treatment was performed at 300 ° C. for 3 minutes to form a CuSn alloy layer as shown in FIG.

2. Composition analysis of CuSn alloy layer (1) Analysis method Composition analysis of the CuSn alloy layer was performed by X-ray diffraction and EDX. The composition of the surface was analyzed by XPS.

(2) Analysis result It was found by composition analysis that Cu ₆ Sn ₅ was formed in the CuSn alloy layer. It was also found that SnO was mainly formed on the surface as an oxide layer, and Cu was present as a metal bond.

3. Removal of oxide layer Next, the oxide layer on the surface of the CuSn alloy layer was removed by immersion in sulfuric acid for 5 minutes.

4). Contact resistance measurement (confirmation of removal of oxide layer)
The contact resistance before and after removal of the oxide layer was measured.

(1) Measurement method Using a gold plating emboss with a radius of 3 mm, the contact resistance at each load when the load was changed and contacted with the gold plating emboss was measured using a four-terminal method (FR test) (N = 3). The energizing current was 10 mA and the maximum load was 40N.

(2) Measurement results The measurement results are shown in FIG. As shown in FIG. 11, the contact resistance of the sample after removal of the oxide layer (after acid treatment) is significantly lower than that of the sample before removal of the oxide layer (before acid treatment). It was confirmed that a certain oxide layer was sufficiently removed.

5. Formation of Conductive Oxide Layer Next, heat treatment was performed at 160 ° C. for 120 hours to form a conductive oxide layer on the surface.

6). Composition analysis of conductive oxide layer (1) Analytical method Composition analysis of the surface after heat treatment was performed by XPS.

(2) Analysis result It was found by composition analysis that Cu, Sn, and O were detected on the outermost surface, and an oxide having a constant Cu and Sn ratio was formed. Cu exists as an oxide CuO _x (specifically, Cu ₂ O) or a metal bond, and Sn mainly exists as an oxide SnO _x (specifically, SnO ₂ ) or a metal bond. I found out.

7). Measurement of contact resistance The contact resistance before and after the heat treatment was measured in the same manner as described above (N = 3). The measurement results are shown in FIG. As shown in FIG. 12, the change in contact resistance is small before and after the heat treatment. This is because a conductive oxide layer is formed on the surface of the CuSn alloy layer.

  While the present invention has been described based on the embodiments, the present invention is not limited to the above embodiments. Various modifications can be made to the above-described embodiments within the same and equivalent scope as the present invention.

DESCRIPTION OF SYMBOLS 1 Base material 2 Diffusion barrier layer 3 Metal layer 4 Conductive oxide layer or conductive hydroxide layer

Claims (17)

A metal layer forming step of forming a metal layer made of Ni, Sn, Al, Zn, Cu, In or an alloy thereof on the substrate;
An oxide layer removing step of removing the oxide layer of nonconductive formed after the metal layer forming step,
Wherein the surface of the metal layer oxide layer is removed by oxidizing, it has a conductive oxide layer forming step of forming a conductive oxide layer,
Production method of the oxide layer removing step, etching with an acid or alkali, electrolytic etching, dry etching or connector for electrical contact material, characterized in step der Rukoto of removing the oxide layer by mechanical polishing. A metal layer forming step of forming a metal layer made of Ni, Sn, Al, Zn, Cu, In or an alloy thereof on the substrate;
An oxide layer removing step of removing the oxide layer of nonconductive formed after the metal layer forming step,
Said surface of the oxide layer and the metal layer is removed and treated hydroxide, have a conductive hydroxide layer formation step of forming a conductive hydroxide layer,
The method for producing an electrical contact material for a connector, wherein the oxide layer removing step is a step of removing the oxide layer by acid or alkali etching, electrolytic etching, dry etching or mechanical polishing . The metal layer forming step is a step of forming a NiSn alloy layer;
The conductive oxide layer forming step, forming a _NiO x (x ≠ 1) or a mixture of _NiO x (x ≠ 1) and _SnO y (y ≠ 1) are formed from the compounds of _SnO y (y ≠ 1) The method for producing an electrical contact material for a connector according to claim 1, wherein The metal layer forming step is a step of forming a CuSn alloy layer;
The conductive oxide layer forming step, forming a _CuO x (x ≠ 1) or a mixture of _CuO x (x ≠ 1) and _SnO y (y ≠ 1) are formed from the compounds of _SnO y (y ≠ 1) The method for producing an electrical contact material for a connector according to claim 1, wherein The metal layer forming step is a step of forming a NiSn alloy layer;
Wherein the conductive hydroxide layer formation step is a step of forming a Ni _{(OH) 2} and Sn _(OH) a mixture of ₂ or Ni _{(OH) 2} and Sn _(OH) compound formed from ₂ The manufacturing method of the electrical contact material for connectors of Claim 2. The metal layer forming step is a step of forming a CuSn alloy layer;
Wherein the conductive hydroxide layer formation step is a step of forming a Cu _{(OH) 2} and Sn _(OH) a mixture of ₂ or Cu _{(OH) 2} and Sn _(OH) compound formed from ₂ The manufacturing method of the electrical contact material for connectors of Claim 2.   The method for producing an electrical contact material for a connector according to claim 3 or 5, wherein the step of forming the NiSn alloy layer is a step of forming a NiSn alloy layer using an alloy plating bath.   The method for producing an electrical contact material for a connector according to claim 4 or 6, wherein the step of forming the CuSn alloy layer is a step of forming a CuSn alloy layer using an alloy plating bath.   6. The step of forming the NiSn alloy layer is a step of forming a NiSn alloy layer by heat-treating after laminating one or more Ni layers and Sn layers, respectively. Manufacturing method for electrical contact materials for connectors.   7. The step of forming the CuSn alloy layer is a step of forming a CuSn alloy layer by performing heat treatment after laminating one or more Cu layers and Sn layers, respectively. Manufacturing method for electrical contact materials for connectors.   The method for producing an electrical contact material for a connector according to claim 9, wherein the Ni layer and the Sn layer are formed by electroplating.   The method for producing an electrical contact material for a connector according to claim 10, wherein the Cu layer and the Sn layer are formed by an electroplating method.   The method for producing an electrical contact material for a connector according to claim 9, wherein the Ni layer and the Sn layer are formed by vapor deposition.   The method for producing an electrical contact material for a connector according to claim 10, wherein the Cu layer and the Sn layer are formed by vapor deposition.   15. The electrical contact material for a connector according to claim 2, wherein a Ni layer is provided on the substrate prior to the formation of the NiSn alloy layer or the CuSn alloy layer. Method.   The method for producing an electrical contact material for a connector according to any one of claims 2 to 15, wherein the oxide layer removing step is a step of removing the oxide layer with a Sn plating stripping solution. . The said base material is Cu, Al, Fe, or these alloys, The manufacturing method of the electrical contact material for connectors of any one of Claim 1 thru | or 16 characterized by the above-mentioned.

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