JP2009099548A - Silver-clad composite material for movable contact and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide silver-clad composite material for a movable contact and its manufacturing method, which provide a long-life movable contact by preventing peeling of a silver clad layer even in repeated switching action of a contact and suppressing an increase of contact resistance even in prolonged use while maintaining good workability in press working or the like, and furthermore capable of improving yields of products dramatically. <P>SOLUTION: The silver-clad composite material 100 for a movable contact comprises a base 110 made of an iron- or nickel-base alloy, an under layer 120 formed out of any one selected from among nickel, cobalt, a nickel alloy, and a cobalt alloy on at least part of a surface of the base 110, an intermediate layer 130 formed out of copper or a copper alloy on the under layer 120, and an outermost layer 140 formed out of silver or a silver alloy on the intermediate layer 130. An uneven part 150 is formed on an interface of the under layer 120 and the intermediate layer 130 to improve adhesiveness of the under layer 120 and the intermediate layer 130. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a silver-coated composite material used for a movable contact and a method for producing the same, and more particularly to a silver-coated composite material capable of obtaining a long-life movable contact and a method for producing the same.

  A disc spring contact, a brush contact, a clip contact or the like is used for an electrical contact portion such as a connector, a switch, or a terminal. For these contacts, nickel is ground-plated on a base material such as copper alloy and stainless steel including iron and nickel alloys, which are relatively inexpensive and excellent in corrosion resistance, mechanical properties, etc., and then conductive and solder A silver-coated composite material coated with silver having excellent attachment properties is frequently used (see Patent Document 1).

  In particular, silver-coated composite materials using stainless steel substrates are advantageous for miniaturization of contacts because they have better mechanical properties and fatigue life than those using copper alloy substrates, and the number of operations can be increased. Therefore, it is used for movable contacts such as long-acting tactile push switches and detection switches.

  However, the silver-coated composite material, in which nickel is coated on a stainless steel substrate and silver is coated on it, has a large contact pressure of the switch. There was a problem that it was easy to do. This phenomenon is understood to occur for the following reasons.

  In a silver-coated composite material 900 illustrated in FIG. 7, a base layer 902 and an outermost layer 903 are formed on a base material 901 made of stainless steel (FIG. 7A). The nickel that forms the underlayer 902 and the silver that forms the outermost layer 903 have a property that they do not dissolve in each other, and the outermost layer 903 undergoes a phenomenon in which oxygen enters and diffuses from the atmosphere. Therefore, oxygen that has entered and diffused into the outermost layer 903 reaches the interface between the lower layer 902 and the uppermost layer 903, and in order to generate nickel oxide 904, the oxygen between the lower layer 902 and the outermost layer 903 The adhesion is reduced ((b) in the figure).

As a means for solving the above-mentioned problems, a silver-coated composite material in which a base layer (nickel layer), an intermediate layer (copper layer), and an outermost layer (silver layer) are electroplated in this order on a stainless steel substrate (Patent Document 2) -5) has been proposed. An example of a silver-coated composite material formed using these techniques is shown in FIG. The silver-coated composite material 910 has an intermediate layer formed between copper, which is solid-dissolved in both nickel and silver, between the base layer 912 and the outermost layer 914 formed in nickel and silver, which are not solid-dissolved in each other. It is provided as a layer 913 (FIG. 7). Thereby, it is possible to improve the adhesion between the respective layers by causing mutual diffusion between the intermediate layer 913 and each of the layers 912 and 914. Furthermore, the effect of preventing the deterioration of adhesion due to the accumulation of oxygen at the interface is captured by trapping the oxygen that has entered from the atmosphere and diffused in the outermost layer 914 into the copper that has been dissolved in the outermost layer 114 from the intermediate layer 113. And can prevent a decrease in adhesion.
JP 59-219945 A JP 2004-263274 A JP 2005-2400 A JP 2005-133169 A JP 2005-174788 A

  However, it has become clear that the above technique has the following drawbacks. That is, compared to the conventional silver-coated composite material formed by electroplating a nickel layer and a silver layer in this order, when the intermediate layer made of copper is formed, the contact resistance increases more quickly when used for a long time. There is a problem of becoming. In addition, if at least one of the underlayer (nickel layer) or the intermediate layer (copper layer) is too thick, the flexibility of these layers will decrease, resulting in cracks in at least one of the underlayer or intermediate layer during pressing. It has also been found that it causes problems such as entering. In addition, there is a limit to improving the adhesion at the interface between the underlayer and the intermediate layer, and considering the fact that press workability is kept good, a new problem arises in that the yield in product production becomes extremely worse. I understood it.

  The present invention has high workability with respect to press working, etc., and the silver coating layer does not peel off even when the opening / closing operation is repeatedly performed using a movable contact, and an increase in contact resistance is suppressed even in long-term use. It is an object of the present invention to provide a silver-coated composite material for a movable contact and a method for producing the same, which can provide a movable contact with a long life and can dramatically improve the adhesion between layers.

  As a result of diligent research in view of such a situation, the present inventors have found that copper dissolved in the outermost layer from the intermediate layer reaches the surface of the outermost layer, where it is oxidized to produce an oxide with high electrical resistance. Therefore, it was ascertained that an increase in contact resistance occurred (FIG. 8). As a means for solving such a problem, it has been found that an increase in contact resistance can be prevented by reducing the amount of copper reaching the surface of the outermost layer by reducing the thickness of the intermediate layer. Further, it has been found that by making the underlayer and the intermediate layer thin, it is possible to suppress cracks during press working and to suppress an increase in contact resistance during repeated opening and closing operations of the contacts. Furthermore, it has been found that the adhesion at the interface between the underlayer and the intermediate layer can be significantly improved by forming, for example, wavy irregularities at the interface between the underlayer and the intermediate layer. The present invention has been made based on the above-described findings.

  According to a first aspect of the silver-coated composite material for a movable contact of the present invention, a base material made of an alloy mainly composed of iron or nickel, and nickel, cobalt, nickel formed on at least a part of the surface of the base material An underlayer made of any one of an alloy and a cobalt alloy, an intermediate layer made of copper or a copper alloy formed on the underlayer, and a silver or silver alloy formed on the intermediate layer. And an unevenness is formed at the interface between the base layer and the intermediate layer.

  According to a second aspect of the silver-coated composite material for a movable contact of the present invention, irregularities are formed at the interface between the intermediate layer and the outermost layer.

  According to a third aspect of the silver-coated composite material for a movable contact of the present invention, the total thickness of the base layer and the intermediate layer is in the range of 0.025 to 0.20 μm. .

  According to a fourth aspect of the silver-coated composite material for movable contacts of the present invention, the substrate is made of stainless steel.

  The first aspect of the method for producing a silver-coated composite material for a movable contact according to the present invention is to activate a metal strip substrate made of an alloy mainly composed of iron or nickel by electrolytic degreasing and pickling with hydrochloric acid. The first step, and then applying nickel plating on the base material by electrolysis with an electrolytic solution containing nickel chloride and free hydrochloric acid, or adding cobalt chloride to the electrolytic solution containing nickel chloride and free hydrochloric acid A second step of forming a base layer having irregularities on the surface by performing a plating process of either nickel alloy plating, and then electrolysis with an electrolytic solution containing copper sulfate and free sulfuric acid on the base layer Apply copper plating, or use copper cyanide or potassium cyanide as a base, add zinc cyanide or potassium stannate, and electrolyze and apply copper alloy plating to form an intermediate layer A third step; On the intermediate layer, silver plating is performed by electrolysis with an electrolytic solution containing silver cyanide and potassium cyanide, or antimonyl potassium tartrate is added to the electrolytic solution containing silver cyanide and potassium cyanide to form a silver alloy plating. A silver-coated composite material in which irregularities are formed at the interface between the underlayer and the intermediate layer is manufactured by a process including a fourth process of forming an outermost layer by performing any one of the plating processes It is characterized by that.

  According to a second aspect of the method for producing a silver-coated composite material for movable contacts of the present invention, either the copper plating or the copper alloy plating is performed, and then either the silver plating or the silver alloy plating is performed. Before the plating treatment is performed, silver strike plating is performed by electrolysis with an electrolytic solution containing silver cyanide and potassium cyanide to produce a silver-coated composite material.

  A third aspect of the method for producing a silver-coated composite material for a movable contact according to the present invention includes a base material made of an alloy mainly composed of iron or nickel, nickel formed on at least a part of the surface of the base material, Formed on the intermediate layer made of any one of cobalt, nickel alloy and cobalt alloy, having an underlayer having irregularities on the surface, an intermediate layer made of copper or a copper alloy formed on the underlayer, and A method for producing a silver-coated composite material for a movable contact comprising an outermost layer made of silver or a silver alloy, wherein the base material is electrolytically degreased and then contains at least one of nickel ions and cobalt ions The underlayer is formed by an activation process that is activated by pickling.

  In a fourth aspect of the method for producing a silver-coated composite material for a movable contact according to the present invention, a base material made of an alloy containing iron or nickel as a main component is electrolytically degreased, and then contains at least one of nickel ions and cobalt ions. A first step of forming on the substrate a base layer made of any one of nickel, cobalt, a nickel alloy, and a cobalt alloy and having irregularities on the surface by an activation treatment that is activated by pickling with an acidic solution. Then, the base layer is electroplated with an electrolytic solution containing copper sulfate and free sulfuric acid, or plated with copper, or based on copper cyanide and potassium cyanide, and added with zinc cyanide or potassium stannate for electrolysis. A second step of forming an intermediate layer by performing a plating treatment of either copper alloy plating, and then, silver cyanide and potassium cyanide are included on the intermediate layer The outermost layer is formed by either silver plating by electrolysis in the solution or by adding silver alloy plating by adding potassium antimonyl tartrate to the electrolyte containing silver cyanide and potassium cyanide. And a third step of manufacturing a silver-covered composite material in which irregularities are formed at an interface between the base layer and the intermediate layer.

In a fifth aspect of the method for producing a silver-coated composite material for a movable contact according to the present invention, the cathode current density during the activation treatment is set within a range of 2.5 to 4.0 (A / dm ² ). Features.

  According to a sixth aspect of the method for producing a silver-coated composite material for movable contacts of the present invention, the substrate is a metal strip.

  According to a seventh aspect of the method for producing the silver-coated composite material for movable contacts of the present invention, the base material is made of stainless steel. According to this structure, the base layer which has an unevenness | corrugation on the surface can be formed on a base material at the time of the activation process of stainless steel.

The present invention has high workability with respect to press working, etc., and the silver coating layer does not peel off even when the opening / closing operation is repeatedly performed using a movable contact, and an increase in contact resistance is suppressed even in long-term use. It is possible to provide a silver-coated composite material for a movable contact and a method for producing the same, which can provide a movable contact having a long life and can dramatically improve the adhesion between layers.
According to the present invention, since the unevenness is formed at the interface between the underlayer and the intermediate layer, the contact area between the two increases, and the adhesion between the underlayer and the intermediate layer is improved by mutual diffusion. . Furthermore, when the unevenness | corrugation is formed in the interface of an intermediate | middle layer and an outermost layer, the effect that both adhesiveness improves by the mutual diffusion between an intermediate | middle layer and an outermost layer is also acquired.

  Preferred embodiments of the silver-coated composite material for movable contacts and the method for producing the same according to the present invention will be described in detail.

(First embodiment of silver-coated composite material for movable contact)
A first embodiment of the silver-coated composite material for movable contacts of the present invention will be described with reference to the cross-sectional view shown in FIG. A silver-coated composite material 100 for a movable contact according to the present embodiment includes a base 110 made of an alloy mainly composed of iron or nickel, a base layer 120 formed on at least a part of the surface of the base 110, and a base layer. An intermediate layer 130 formed on 120 and an outermost layer 140 formed on the intermediate layer 130 are provided.

  In this embodiment, stainless steel is used as the base material 110 made of an alloy containing iron or nickel as a main component. Here, the alloy containing iron or nickel as a main component means an alloy having a mass ratio of at least one of iron and nickel of 50% by mass or more. As the stainless steel used for the base material 110 that bears the mechanical strength of the movable contact, a rolled tempered material or a tension annealing material such as SUS301, SUS304, SUS305, or SUS316 that is excellent in stress relaxation characteristics and fatigue fracture resistance is preferable.

  The underlayer 120 formed on the stainless steel substrate 110 is formed of any one of nickel, cobalt, a nickel alloy, and a cobalt alloy. The underlayer 120 is disposed in order to improve the adhesion between the stainless steel used for the substrate 110 and the intermediate layer 130. The intermediate layer 130 is made of copper or a copper alloy, and is arranged to improve the adhesion between the foundation layer 120 and the outermost layer 140. Further, another layer may be provided between the base layer 120 and the substrate 110 for a specific purpose.

  As a metal for forming the underlayer 120, nickel, cobalt, or an alloy containing these as main components (50% by mass or more as a whole mass ratio) is used, and nickel is particularly preferable. The underlayer 120 can be formed by electrolysis using, for example, an electrolytic solution containing nickel chloride and free hydrochloric acid using the base 110 made of stainless steel as a cathode. About the thickness of a base layer, it is preferable that an average value shall be 0.001-0.04 micrometer. More preferably, it is 0.001-0.009 micrometer. Hereinafter, an example in which nickel is used as the metal of the underlayer 120 will be described. However, not only nickel but also any of cobalt, a nickel alloy, and a cobalt alloy, the same effect as described below can be obtained. It is done.

  The cause of workability deterioration in the conventional silver-coated composite material is that at least one of the base layer and the intermediate layer is too thick, and the flexibility of these layers is reduced. As a countermeasure, in this embodiment, the surface of the base 110 and the base layer 120, the base layer 120 and the intermediate layer 130, and the base layer 120 and It is effective to make the intermediate layer 130 thinner. When the average value of the thickness of the underlayer 120 is set to 0.04 μm or less, there is no possibility that the workability is lowered by the underlayer 120.

  In the present embodiment, in order to improve the adhesion between the base layer 120 and the intermediate layer 130, the unevenness 150 is formed at the interface between them. By forming the projections and depressions 150, the contact area between the base layer 120 and the intermediate layer 130 can be increased, thereby improving adhesion by mutual diffusion between the two. In the silver-coated composite material 100 for a movable contact shown in FIG. 1, as an example, the interface between the base layer 120 and the intermediate layer 130 is formed in a wavy unevenness 150.

  On the other hand, the cause of the conventional increase in contact resistance is that the intermediate layer copper diffused in the outermost silver coating layer reaches the surface of the outermost layer and is oxidized. That is, as shown in FIG. 9, as an example, copper dissolved in the outermost layer 914 from the intermediate layer 913 reaches the surface of the outermost layer 914 and is oxidized to form an oxide 915 having a high electrical resistance. An increase in resistance occurred.

  In order to solve such a problem, in this embodiment, the range in which the adhesion between the surface of the substrate 110 and the underlayer 120, the underlayer 120 and the intermediate layer 130, and the intermediate layer 130 and the outermost layer 140 is maintained. Thus, a suitable thickness of the intermediate layer 130 is determined such that the copper of the intermediate layer 130 does not reach the surface of the outermost layer 140. In the present embodiment, the total average thickness DT obtained by adding the average thickness D2 of the intermediate layer 130 to the average thickness D1 of the base layer 120 is in the range of 0.025 to 0.20 μm.

  Thereby, the diffusion of copper to the surface of the outermost layer 140 and the accompanying oxidation can be suppressed while maintaining high adhesion between the respective layers. The most desirable form as the outermost layer is a configuration in which a silver or silver alloy layer containing copper only in the vicinity of the intermediate layer and not including copper in the vicinity of the surface is formed. The outermost layer thickness D3 is preferably 0.5 to 1.5 μm.

  From the viewpoint of improving workability, it is preferable to make the underlayer 120 and the intermediate layer 130 thin. However, a lower limit of 0.06 μm is provided for the total DT of the average thickness of the underlayer 120 and the average thickness of the intermediate layer 130. If the value is below this value, the effect of increasing the adhesion between the surface of the base 110 and the underlayer 120, the underlayer 120 and the intermediate layer 130, and the intermediate layer 130 and the outermost layer 140 is reduced. It is. In addition, the upper limit value of 0.20 μm is provided for the total thickness DT of the average thickness of the base layer 120 and the average thickness of the intermediate layer 130. If this value is exceeded, the contact resistance in the use environment tends to increase. Is due to. By setting the average thickness D1 of the underlayer 120 and the average thickness D2 of the intermediate layer 130 within the above-described ranges, cracking of each layer during press working can be prevented.

  For the base layer 120, the intermediate layer 130, and the outermost layer 140 of the silver-coated composite material 100 for movable contacts of this embodiment, any method such as electroplating, electroless plating, physical / chemical vapor deposition, or the like is used. Among them, the electroplating method is most advantageous from the viewpoint of productivity and cost. Each of the above-described layers may be formed on the entire surface of the stainless steel substrate 110, but it is more economical to form only the contact portions. In addition, a known method such as heat treatment can be applied in order to improve the adhesion strength between the layers.

  In addition, you may make it alloy copper into layers other than the intermediate | middle layer 130 formed with copper or copper alloy. In that case, the amount of copper in the intermediate layer 130 may be reduced by an amount corresponding to the alloyed copper. Further, an underlayer may be further provided under the nickel layer for other purposes. In this case, even if copper is contained in the underlayer formed under the nickel layer, the underlayer copper formed under the nickel layer hardly contributes to diffusion to the outermost silver layer. .

(Second embodiment of silver-coated composite material for movable contact)
A second embodiment of the silver-coated composite material for movable contacts of the present invention will be described with reference to the cross-sectional view shown in FIG. Similarly to the silver-coated composite material for movable contacts 100 of the first embodiment, the silver-coated composite material for movable contacts of the present embodiment is composed of a base material 210 made of an alloy containing iron or nickel as a main component, and a base material 210. A base layer 220 formed on at least a part of the surface of the substrate, an intermediate layer 230 formed on the base layer 220, and an outermost layer 240 formed on the intermediate layer 230.

  Also in this embodiment, in order to improve the adhesion between the base layer 220 and the intermediate layer 230, the unevenness 250 is formed at the interface between them, but in addition to this, the interface between the intermediate layer 230 and the outermost layer 240 is also formed. Unevenness 260 is formed. Thereby, the contact area of the intermediate | middle layer 230 and the outermost layer 240 can be increased, and the adhesiveness improvement by mutual diffusion between both can be aimed at.

  As described above, in the silver-coated composite material 200 for the movable contact according to the second embodiment shown in FIG. 2, the unevenness 250 is formed at the interface between the foundation layer 220 and the intermediate layer 230, and the intermediate layer 230 and the outermost layer 240 are formed. By forming the unevenness 260 at the interface, the adhesion at each interface can be improved.

(First embodiment of manufacturing method of silver-coated composite material for movable contact)
1st Embodiment of the manufacturing method of the silver covering composite material for movable contacts which manufactures the silver covering composite material 100 for movable contacts which concerns on the said one embodiment is described below using the flowchart shown in FIG. In FIG. 3, the manufacturing method of this embodiment is demonstrated taking the silver covering composite material 100 for movable contacts as an example.

  In the manufacturing method of the present embodiment, as a first step, the stainless steel strip used as the substrate 110 is cathodic electrolytically degreased in an alkaline solution such as sodium orthosilicate or caustic soda, and then pickled with hydrochloric acid to activate (FIG. 3 S1).

In the next second step, the base layer 120 is formed by electrolyzing with an electrolytic solution containing nickel chloride and free hydrochloric acid at a cathode current density ( ^{2 to} 5 A / dm ² ) and performing nickel plating (FIG. 3). S2). Here, for example, by controlling the current density of the current flowing through the substrate 110, it is possible to perform nickel plating with the surface 150 as the base layer 120 on the surface of the substrate 110. It is possible to perform nickel plating with unevenness 150 on the surface as the underlayer 120 on the surface of the substrate 110 by other methods, for example, a method of controlling the flow of the plating solution, and by any method, The reproducibility is enhanced when the maximum thickness of the underlayer 120 is 0.04 μm or less. In this case, the surface roughness (maximum roughness: Rmax) of the foundation layer 120 is a value smaller than the value of the maximum thickness of the foundation region 120. In addition, as electrolyte solution of said nickel plating, the electrolyte solution which added nickel sulfamate (100-150 g / liter) and boron (20-50 g / liter), and adjusted pH in the range of 2.5-4.5. May be used.

In the next third step, an intermediate layer 130 is formed by electrolysis with an electrolytic solution containing copper sulfate and free sulfuric acid at a cathode current density (5 A / dm ² ) and copper plating (S 3 in FIG. 3). ).

In the final fourth step, the outermost layer 140 is formed by electrolysis with an electrolytic solution containing silver cyanide and potassium cyanide at a cathode current density ( ^{2 to} 15 A / dm ² ) and silver plating (FIG. 3). S4). By such processing from the first step S1 to the fourth step S4, the silver-coated composite material 100 for movable contacts can be manufactured.

In the second step S2 for forming the underlayer 120, cobalt chloride is added to an electrolytic solution containing nickel chloride and free hydrochloric acid instead of the nickel plating, and the cathode current density ( ^{2 to} 5 A / dm ² ). Nickel alloy (nickel-cobalt alloy) plating may be applied by electrolysis. Further, in the third step S3 for forming the intermediate layer 130, instead of the above copper plating, copper cyanide and potassium cyanide are basically used, and the cathode current density (2 to 5 A / dm) is added by adding zinc cyanide or potassium stannate. ² )) and electroplating with copper alloy (copper-zinc alloy or copper-tin alloy). Prior to the third step S3 or as an alternative to the third step S3, copper strike plating is performed by electrolysis with an electrolytic solution containing copper sulfate and free sulfuric acid at a cathode current density (1 to 3 A / dm ² ). May be applied. By performing copper strike plating on at least a portion in contact with the underlayer 120 in the intermediate layer 130, the adhesion between the underlayer 120 and the intermediate layer 130 is improved, and the intermediate layer 130 is densely formed. The outermost layer 140 to be formed is also densely formed, and it is possible to prevent the surface roughness at the interface between the layers from becoming so large as to cause cracking during press working. That is, by performing copper strike plating, the effect of preventing cracking of each layer during press working is further exhibited.

Further, in the fourth step S4 for forming the outermost layer 140, in place of the above silver plating, antimonyl potassium tartrate is added to an electrolytic solution containing silver cyanide and potassium cyanide, and the cathode current density (2 to 5 A / dm. ² ), electrolysis and silver alloy (silver-antimony alloy) plating may be performed. Alternatively, after the copper plating or copper alloy plating in the third step S3, electrolysis is performed at an anode current density (1 to 5 A / dm ² ) with an electrolytic solution containing silver cyanide and potassium cyanide, and then silver strike plating is performed. Silver plating or silver alloy plating may be applied.

(Example 1 of the manufacturing method according to the first embodiment)
The silver-coated composite material 100 for movable contacts and the manufacturing method thereof according to the above embodiment will be described in more detail using examples.
In the following examples, strip-shaped stainless steel SUS301 (hereinafter referred to as SUS301 strip) is used as the substrate 110, and the dimensions of the SUS301 strip are 0.06 mm thick and 100 mm strip width. In a plating line for continuously winding and winding SUS301, the first step of electrolytically degreasing SUS301, washing with water, electrolytically activating and washing with water, nickel plating (or nickel-cobalt plating) and water washing treatment Each of the 2nd process to perform, the 3rd process to perform processing of copper plating and water washing, and the 4th process to perform each processing of silver strike plating, silver plating, water washing, and drying is carried out.

The processing conditions for each step are as follows.
1. First step (electrolytic degreasing, electrolytic activation)
The stainless steel strip is subjected to cathodic electrolytic degreasing with an aqueous solution of sodium orthosilicate 70 to 150 g / liter (100 g / liter in this embodiment) or caustic soda 50 to 100 g / liter (70 g / liter in this embodiment), and pickled with 10% hydrochloric acid. To activate.

2. Second step (1) In the case of nickel plating
A cathode current density of 2 to 5 A / liter with an electrolyte containing 10 to 50 g / liter of nickel chloride hexahydrate (25 g / liter in this example) and 30 to 100 g / liter of free hydrochloric acid (50 g / liter in this example). Electrolytic plating is performed at dm ² (3 A / dm ² in this embodiment).

(2) In the case of nickel alloy plating Cobalt chloride hexahydrate or cupric chloride dihydrate is added to the above plating solution, and the cobalt ion concentration or copper ion concentration in the plating solution is nickel ion and cobalt ion or The plating is carried out so that the concentration corresponds to 5 to 20% of the concentration of copper ions added (10% in this embodiment).

3. Third step (1) In the case of copper strike plating: Copper sulfate pentahydrate 10-30 g / liter (15 g / liter in this embodiment) and free sulfuric acid 50-150 g / liter (100 g / liter in this embodiment) (in this example 2A / dm ²⁾ cathode current density. 1-3A / dm ² in an electrolytic solution containing plating by electrolyzing with.

(2) In the case of copper plating An electrolytic solution containing 20 to 60 g / liter of copper sulfate pentahydrate (40 g / liter in this embodiment) and 50 to 150 g / liter of free sulfuric acid (100 g / liter in this embodiment). Electrolytic plating is performed at a cathode current density of ^{2 to} 6 A / dm ² (5 A / dm ² in this embodiment).

(3) In the case of copper alloy plating Copper cyanide 30 to 70 g / liter (50 g / liter in this embodiment), potassium cyanide 50 to 100 g / liter (75 g / liter in this embodiment), potassium hydroxide 30 to 50 g / liter (40 g / liter in this embodiment), zinc cyanide 0.2 to 0.4 g / liter (0.3 g / liter in this embodiment) or potassium stannate 0.5 to 2 g / liter (this embodiment) In the example, 1 g / liter) is added and electrolysis is performed at a cathode current density of ^{2 to} 5 A / dm ² (3 A / dm ² in this embodiment).

4). Fourth Step (1) In the case of silver strike plating An electrolyte containing 3 to 7 g / liter of silver cyanide (5 g / liter in this embodiment) and 30 to 70 g / liter of potassium cyanide (50 g / liter in this embodiment). (in this example 2A / dm ²⁾ cathode current density. 1-3A / dm ² plating by electrolyzing with.

(2) In the case of silver plating Cathodic current density 2 with an electrolyte containing 30 to 100 g / liter of silver cyanide (50 g / liter in this embodiment) and 30 to 100 g / liter of potassium cyanide (50 g / liter in this embodiment) Electrolysis is performed at -15 A / dm ² (5 A / dm ² in this embodiment). In addition, you may add 20-40 g / liter of potassium carbonate (30 g / liter in a present Example) as needed.
(3) In the case of silver alloy plating 0.3 to 1 g / liter of potassium antimonyl tartrate (0.6 g / liter in this embodiment) is added to the above electrolytic solution and electrolyzed and plated.

  Table 1 shows samples in which the thickness of the underlayer 120, the thickness of the intermediate layer 130, and the thickness of the outermost layer 140 were variously changed. Here, the difference between the maximum value and the minimum value of the thickness of the underlayer 120 divided by the average value of the thickness of the underlayer 120 (the arithmetic average value measured at any 10 points) is the unevenness difference ( %), And the current density of the current flowing through the substrate 110 was controlled so that the unevenness difference was 30%. The unevenness difference values are shown in Table 1. In addition, sample No. of the Example shown in Table 1 is shown. Samples 49 to 52 were heat-treated at 250 ° C. for 2 hours in an argon (Ar) gas atmosphere.

  A switch 300 having the structure shown in FIGS. 4 and 5 was manufactured using the silver-coated composite material for movable contacts shown in Table 1 manufactured under the above processing conditions. 4 is a plan view of the switch 300, and FIG. 5 is a cross-sectional view of the switch 300 taken along the line AA shown in FIG.

  The dome-shaped movable contact 310 shown in the figure is formed by processing a silver-coated composite material for movable contacts of the embodiment shown in Table 1 into a diameter of 4 mmφ, and the fixed contacts 320a and 320b are made of brass strip. Are formed by plating silver to a thickness of 1 μm. The dome-shaped movable contact 310 is covered with a resin filler 330 and is housed in the resin case 340 together with the fixed contact 320. The switch 300 is in an OFF state when the dome-shaped movable contact 310 shown in FIG. 5A is in a convex state, and as shown in FIG. 5B, the dome-shaped movable contact 310 is pressed and fixed. The contact point 320a and the contact point 320b are turned on when they are electrically connected.

Using the switch 300 as described above, the key-on test was performed by repeating the on / off state shown in FIG. In the keystroke test, keystrokes are performed a maximum of 2 million times at a contact pressure of 9.8 N / mm ² and a keystroke speed of 5 Hz. With respect to the dome-shaped movable contact 310, the results of measuring the change over time in the contact resistance during the keystroke test are the initial values, after one million keystrokes (1 after keystroke), after 2 million keystrokes (2 after keystroke), Each is shown in Table 2. Further, after finishing the keystroke test of 2 million times, the dome-shaped movable contact 310 was observed for the presence or absence of cracks, and the results are also shown in Table 2. In addition, if the value of contact resistance is 100 mΩ or less, there is no problem in practical use.

  In the heating test, all samples were heated for 1000 hours in an air bath at 85 ° C., and the change in contact resistance was measured. The results are shown in Table 2.

Sample No. of the example shown in Table 1 1 to 52, as shown in Table 2, the increase in contact resistance is small even if the key hit test is performed 2 million times, and the exposure of the intermediate layer and the underlayer is not seen at the contact portion after 2 million times the key press. I couldn't. Furthermore, even after 1000 hours of heating, the increase in contact resistance was small, and the values of contact resistance were 100 mΩ or less for all the samples, and there was no practical problem.

  In contrast, Sample No. of Comparative Example in which the sum of the thickness of the underlayer 120 and the thickness of the intermediate layer 130 is less than 0.025 μm. In No. 101, deterioration of workability due to a decrease in the adhesion of each layer was observed, and the sample No. of the comparative example in which the thickness of the underlayer 120 was larger than the upper limit of the range of the present invention (0.05 μm or more). . In 102-108, the tendency for workability to be inferior was seen. In addition, sample No. In 101 to 108, an increase in contact resistance (specifically, a state in which the value of the contact resistance exceeds 100 mΩ), which seems to be caused by poor workability, was detected after 2 million keystrokes.

  Furthermore, sample No. of the comparative example. 101 to 108, a crack at the contact portion that was thought to be caused by inferior workability was found, and the sample No. of Comparative Example in which the thickness of the underlayer 120 was 0.3 μm was found. In 106 to 108, the outermost layer of the contact portion was peeled off and the underlayer was exposed.

  On the other hand, in the samples 103, 105, and 108 in which the thickness of the intermediate layer 120 is 0.3 μm, a significant increase in the contact resistance is observed after the heating test (specifically, the value of the contact resistance exceeds 100 mΩ), Cracks were confirmed after the keystroke test.

(Example 2 of the manufacturing method according to the first embodiment)
Here, Example 2 of the manufacturing method of the silver-coated composite material for movable contacts according to the first embodiment for manufacturing the silver-coated composite material 100 for movable contacts will be described.

  Regarding the underlayer 120: Sample No. 1 in Table 1 was used for nickel alloy plating in which 10% by mass of nickel was replaced with copper or cobalt. 1-52 and no. Tests similar to 101-108 were performed, but the test results were not substantially different from the results shown in Table 2. The same was true for an example in which nickel was completely replaced with cobalt.

  Regarding the intermediate layer 130: In the case of copper alloy plating in which 0.5% by mass of copper was replaced with tin or zinc, sample No. 1 in Table 1 was used. 1-52 and no. Tests similar to 101-108 were performed, but the test results were not substantially different from the results shown in Table 2.

Regarding the outermost layer 140: Sample No. 1 in Table 1 was obtained when the silver alloy plating in which 1% by mass of silver was replaced with antimony was used. 1-52 and no. Tests similar to 101-108 were performed, but the test results were not substantially different from the results shown in Table 2.
Moreover, although the said modification was combined suitably, the test result did not differ substantially from the result shown in Table 2.

(2nd Embodiment of the manufacturing method of the silver covering composite material for movable contacts)
Next, 2nd Embodiment of the silver covering composite material for movable contacts which manufactures the silver covering composite material 100 for movable contacts shown in FIG. 1 is described. In addition, it cannot be overemphasized that this manufacturing method is applicable also to the method of manufacturing the silver covering composite material 200 for movable contacts shown in FIG.
The manufacturing method of the silver covering composite material for movable contacts which concerns on this embodiment has the following process.

(1st process) The base material (base material of a metal strip) 110 which is a stainless steel strip made of an alloy containing iron or nickel as a main component is electrolytically degreased, and then pickled with an acidic solution containing nickel ions and activated. The foundation layer 120 made of nickel and having irregularities 150 on the surface is formed on the substrate 110 by the activation treatment to be converted.
In the first step, an activation process for activating the substrate 110 is performed under the following conditions, for example.

(1) An acidic solution containing 120 g / liter of free hydrochloric acid and 12 g / liter of nickel chloride hexahydrate is used as an acidic solution containing nickel ions. In addition, as an acidic solution containing nickel ions, free hydrochloric acid is 80 to 200 g / liter (more preferably 100 to 150 g / liter), and nickel chloride hexahydrate is 5 to 20 g / liter (more preferably 10 to 15 g / liter). It is preferable to add in the range of 1 liter). When the addition amounts of free hydrochloric acid and nickel chloride hexahydrate are out of the above ranges, the adhesion between the substrate and the underlayer tends to decrease.

(2) The cathode current density during the activation process is set to 3.0 (A / dm ² ). The cathode current density during the activation treatment is preferably in the range of 2.5 to 4.0 (A / dm ² ). If the cathode current density is lower than the lower limit, a missing portion may be formed in the underlayer 120. . Further, when the cathode current density is lower than 2.0 (A / dm ² ), the adhesion between the base material and the base region tends to decrease, which is not preferable. Note that if the cathode current density exceeds 4.0 (A / dm ² ), it may be difficult to form irregularities on the underlayer 120, and if the cathode current density exceeds 5.0 (A / dm ² ). When the base material is stainless steel, it may be affected by the heat generated by the base material, which is not preferable.

  By performing the activation process of the substrate 110 shown in FIG. 6A under such conditions, nickel (Ni) nuclei 120b are formed at predetermined intervals on the entire surface of the substrate 110 (FIG. 6B). In addition, the base layer 120 having the unevenness 150 on the surface is formed on the entire surface of the substrate 110 (see FIG. 6C). In this embodiment, the underlayer 120 made of nickel is formed by activation treatment. However, when the underlayer made of cobalt is formed by similar activation treatment, cobalt ions are formed in the first step. The substrate 110 is activated with an acidic solution containing.

(2nd process) The intermediate | middle layer 130 is formed on the base layer 120 by electrolyzing with the electrolyte solution containing copper sulfate and a free sulfuric acid by a cathode current density (5 A / dm < ² >), and performing copper plating.
(Third Step) The outermost layer 140 is formed on the intermediate layer 130 by electrolysis with an electrolytic solution containing silver cyanide and potassium cyanide to perform silver plating.

  Thus, in the manufacturing method of the silver covering composite material for movable contacts which concerns on this embodiment, the base material 110 is electrolytically degreased, and at the time of the activation process activated by pickling with the acidic solution containing nickel ion after that, An underlayer 120 having irregularities 150 on the surface is formed on the substrate 110. For this reason, the step of nickel plating or nickel alloy plating for forming the underlayer 120 in the method for producing the silver-coated composite material for movable contacts according to the embodiment described above with reference to FIG. 3 (S2 in FIG. 2). Is no longer necessary. Therefore, since the manufacturing process is simplified and the working time is shortened, the silver-coated composite material for movable contacts can be manufactured at low cost.

  In addition, during the activation process of the base material 110 made of stainless steel, the base layer 120 having the unevenness 150 on the surface can be formed on the base material 110. When the underlayer 120 is formed in this way, not only the adhesion between the substrate 110 and the underlayer 120 is improved, but also the adhesion between the underlayer 120 and the intermediate layer 130 is improved, and for a long-life movable contact. A silver-coated composite material can be obtained.

  As samples manufactured by the manufacturing method according to the second embodiment, the thickness of the underlayer 120, the thickness of the intermediate layer 130, and the thickness of the outermost layer 140 are variously similar to the samples of the examples shown in Table 1. What was changed was created, and these were changed to sample no. 201 to 252 (see Table 3). In addition, sample No. of the Example shown in Table 3 was used. Samples 249 to 252 were heat-treated at 250 ° C. for 2 hours in an argon (Ar) gas atmosphere. As a comparative example, Sample No. 301 to 308 (see Table 3) were prepared. In addition, sample No. in Table 3 201-252 are sample Nos. In Table 1. Samples Nos. 1 to 52 having the same layer structure are shown in Table 3. 301 to 308 are sample Nos. Of comparative examples shown in Table 1. 101 to 108 are samples having the same layer structure. The correspondence relationship is the sample No. of the embodiment shown in Table 1. Sample No. with 200 added to Are sample Nos. Of the examples shown in Table 3. It becomes.

  Sample No. manufactured under the above processing conditions. 201-252 and sample no. A switch similar to the switch 200 having the structure shown in FIGS. 3 and 4 was manufactured using silver-coated composite materials 301 to 308 for movable contacts. Other conditions are the same as the sample No. described above. 1-52 and sample no. It was the same as that of the case where the silver coating composite materials for 101-108 movable contacts were used.

Using the switches as described above, the key-on test was performed by repeating the on / off state shown in FIG. In the keystroke test, keystrokes are performed a maximum of 2 million times at a contact pressure of 9.8 N / mm ² and a keystroke speed of 5 Hz. With respect to the dome-shaped movable contact 210, the results of measuring the change over time in the contact resistance during the keystroke test are the initial values, after one million keystrokes (1 after keystroke), after 2 million keystrokes (2 after keystroke), Each is shown in Table 3. Further, after finishing the keystroke test of 2 million times, the dome-shaped movable contact 210 was observed for the presence or absence of cracks, and the results are also shown in Table 3.

  In the heating test, all samples were heated in an air bath at 85 ° C. for 1000 hours, and the change in contact resistance was measured. The results are shown in Table 3.

  Sample No. of the example shown in Table 3 As shown in Table 3, each of Nos. 201 to 252 has a small increase in contact resistance even when the key hit test is performed 2 million times, and the underlying layer 120 and the intermediate layer 130 are exposed at the contact portion after 2 million times the key press. Was not seen. Furthermore, the increase in contact resistance was small even after 1000 hours of heating. In particular, the sample Nos. Of Examples shown in Table 3 were used. 201-252 are sample Nos. Of Examples shown in Table 1. Compared with 1-52, the increase in contact resistance in 2 million keystroke tests and the increase in contact resistance after heating for 1000 hours are small, and the contact resistance value for all samples is 30 mΩ or less, The performance was found to be very good. The various modifications described in Examples 1 and 2 of the manufacturing method according to the first embodiment can also be applied to the manufacturing method according to the second embodiment.

  As described above, according to the present invention, the outermost layer (silver coating layer) is not peeled even in the repeated opening and closing operation of the contacts, and the increase in contact resistance is suppressed even in long-term use, and the product yield is further reduced. It is possible to provide a silver-coated composite material for a movable contact and a method for producing the same that can be dramatically improved. A long-life movable contact can be produced using the silver-coated composite material for a movable contact of the present invention, and the industrial applicability is high.

It is sectional drawing of the silver covering composite material for movable contacts of 1st Embodiment of this invention. It is sectional drawing of the silver covering composite material for movable contacts of 2nd Embodiment of this invention. It is a flowchart which shows the manufacturing method of the silver covering composite material for movable contacts which concerns on 1st Embodiment of this invention. It is a top view of the switch formed using the silver covering composite material for movable contacts of a 1st embodiment. (A) is a figure which shows an OFF state in AA sectional drawing of the switch shown in FIG. 4, (b) is sectional drawing which shows the ON state of the switch. (A)-(c) is a schematic diagram for demonstrating the manufacturing method of the silver covering composite material for movable contacts which concerns on 2nd Embodiment of this invention. (A), (b) is sectional drawing which shows the conventional silver covering composite material. It is sectional drawing which shows another conventional silver covering composite material. It is sectional drawing which shows the oxide formed with another conventional silver covering composite material.

Explanation of symbols

100, 200 Silver-coated composite material for movable contacts 110, 210 Base material 120, 220, 902, 912 Underlayer 130, 230, 913 Intermediate layer 140, 240, 903, 914 Outermost layer 150, 250 Concavity and convexity 300 Switch 310 Dome-shaped movable Contact 320 Fixed contact 330 Filler 340 Resin case 900, 910 Silver-coated composite material 901 Stainless steel substrate 904, 915 Oxide

Claims (11)

A base material made of an alloy mainly composed of iron or nickel;
An underlayer made of any one of nickel, cobalt, nickel alloy and cobalt alloy formed on at least a part of the surface of the substrate;
An intermediate layer made of copper or a copper alloy formed on the underlayer;
An outermost layer made of silver or a silver alloy formed on the intermediate layer,
A silver-coated composite material for a movable contact, wherein irregularities are formed at an interface between the base layer and the intermediate layer. The silver-coated composite material for a movable contact according to claim 1, wherein unevenness is formed at an interface between the intermediate layer and the outermost layer.   The silver-coated composite material for a movable contact according to claim 1 or 2, wherein the total thickness of the underlayer and the intermediate layer is in the range of 0.025 to 0.20 µm. The silver-coated composite material for a movable contact according to any one of claims 1 to 3, wherein the base material is made of stainless steel. A first step of electrolytically degreasing a base material of a metal strip made of an alloy containing iron or nickel as a main component, pickling with hydrochloric acid and activating, and
Next, the substrate is subjected to nickel plating by electrolysis with an electrolytic solution containing nickel chloride and free hydrochloric acid, or nickel alloy plating is performed by adding cobalt chloride to an electrolytic solution containing nickel chloride and free hydrochloric acid. A second step of performing any one of the plating treatments to form a base layer having irregularities on the surface;
Next, the base layer is electroplated with an electrolytic solution containing copper sulfate and free sulfuric acid, or copper plated, or based on copper cyanide and potassium cyanide, and added with zinc cyanide or potassium stannate for electrolysis. A third step of forming an intermediate layer by performing any one of the copper alloy plating processes;
Next, the intermediate layer is subjected to silver plating by electrolysis with an electrolytic solution containing silver cyanide and potassium cyanide, or antimonyl potassium tartrate is added to the electrolytic solution containing silver cyanide and potassium cyanide to form a silver alloy plating. A silver-coated composite material in which irregularities are formed at the interface between the underlayer and the intermediate layer is manufactured by a process including a fourth process of forming an outermost layer by performing any one of the plating processes A method for producing a silver-coated composite material for a movable contact.   After performing the plating treatment of either the copper plating or the copper alloy plating, before performing the plating treatment of the silver plating or the silver alloy plating, electrolysis is performed with an electrolytic solution containing silver cyanide and potassium cyanide. The method for producing a silver-coated composite material for a movable contact according to claim 5, wherein the silver-coated composite material is produced by performing silver strike plating. A base material made of an alloy containing iron or nickel as a main component and any one of nickel, cobalt, a nickel alloy, and a cobalt alloy formed on at least a part of the surface of the base material, and has an uneven surface. A silver-coated composite for a movable contact, comprising: an underlayer; an intermediate layer made of copper or a copper alloy formed on the underlayer; and an outermost layer made of silver or a silver alloy formed on the intermediate layer A method of manufacturing a material,
For the movable contact, characterized in that the base layer is formed by an activation treatment in which the substrate is electrolytically degreased and then activated by pickling with an acidic solution containing at least one of nickel ions and cobalt ions. A method for producing a silver-coated composite material. Electrolytic degreasing of a base material made of an iron or nickel alloy as a main component, and then pickling and activating with an acidic solution containing at least one of nickel ions and cobalt ions, nickel, cobalt, nickel A first step consisting of any one of an alloy and a cobalt alloy, and forming an underlayer having irregularities on the surface on the substrate;
Next, the base layer is electroplated with an electrolytic solution containing copper sulfate and free sulfuric acid, or copper plated, or based on copper cyanide and potassium cyanide, and added with zinc cyanide or potassium stannate for electrolysis. A second step of forming an intermediate layer by performing any one of the copper alloy plating processes;
Next, the intermediate layer is subjected to silver plating by electrolysis with an electrolytic solution containing silver cyanide and potassium cyanide, or antimonyl potassium tartrate is added to the electrolytic solution containing silver cyanide and potassium cyanide to form a silver alloy plating. And a third step of forming an outermost layer by performing any plating treatment, and producing a silver-coated composite material in which irregularities are formed at the interface between the underlayer and the intermediate layer A method for producing a silver-coated composite material for a movable contact. Preparation of the silver-coated composite material for movable contact according to claim 7 or 8, characterized in that in the range of 2.5 to 4.0 the cathode current density during the activation process (A / dm ²⁾ Method.   The method for producing a silver-coated composite material for a movable contact according to any one of claims 7 to 9, wherein the base material is a metal strip.   The method for producing a silver-coated composite material for a movable contact according to claim 10, wherein the substrate is made of stainless steel.

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