TWI557750B - Electrical contact material and manufacturing method thereof - Google Patents

Electrical contact material and manufacturing method thereof Download PDF

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TWI557750B
TWI557750B TW103103893A TW103103893A TWI557750B TW I557750 B TWI557750 B TW I557750B TW 103103893 A TW103103893 A TW 103103893A TW 103103893 A TW103103893 A TW 103103893A TW I557750 B TWI557750 B TW I557750B
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metal layer
alloy
noble metal
electrical contact
plating
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TW103103893A
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TW201532075A (en
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Yoshiaki Kobayashi
Satoshi Suzuki
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Furukawa Electric Co Ltd
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電氣接點材料及其之製造方法 Electrical contact material and method of manufacturing same
本發明係關於一種電氣接點材料及其製造方法。尤其是關於一種利用由相互不同之貴金屬或其合金所構成之2個貴金屬層進行被覆之電氣接點材料及其製造方法。 The present invention relates to an electrical contact material and a method of manufacturing the same. In particular, it relates to an electrical contact material coated with two noble metal layers composed of noble metals different from each other or alloys thereof, and a method for producing the same.
關於電氣接點零件,先前利用有導電性優異之銅或銅合金,但近年來,接點特性不斷提高,使用裸銅或裸銅合金之實例減少,而利用銅或銅合金上進行有各種表面處理之材料。尤其作為大量用作電氣接點材料者,有於電氣接點部位鍍敷有貴金屬之電氣接點材料。其中,金、銀、鈀、鉑、銥、銠、釕等貴金屬由於顯示出穩定性或優異之導電率等,故而被利用於各種電氣接點材料。 Regarding electrical contact parts, copper or copper alloys having excellent electrical conductivity have been used in the past, but in recent years, contact characteristics have been continuously improved, and examples using bare copper or bare copper alloys have been reduced, and various surfaces have been used on copper or copper alloys. The material to be processed. In particular, as a large number of materials used as electrical contact materials, there are electrical contact materials in which precious metal is plated on the electrical contact portions. Among them, precious metals such as gold, silver, palladium, platinum, rhodium, ruthenium, iridium, etc. are used for various electrical contact materials because of exhibiting stability or excellent electrical conductivity.
作為最近之電氣接點材料,對於適於汽車車載之室內外滑動接點、或磁簧開關(reed switch)、攝影機座架(camera mount)接點用開關等,係利用作為例如除藉由推壓之通常之接觸式以外亦伴隨反覆滑動之電氣接點材料而耐摩耗性良好之電氣接點材料。關於耐摩耗性之提高,作為通用者一般為使用有硬質銀或硬質金之電氣接點材料。進而亦研究開發出分散有微粒子之鍍敷或包覆材料等,開發出謀求提高電氣接點材料之滑動特性等而實施有各種表面處理之電氣接點材料。 As a recent electrical contact material, for indoor and outdoor sliding contacts suitable for automobile vehicles, or a reed switch, a camera mount contact switch, etc., In addition to the usual contact type, the electrical contact material is also resistant to abrasion with the electrical contact material that slides over. As for the improvement of wear resistance, it is generally used as an electrical contact material having hard silver or hard gold. Further, research and development of plating or coating materials in which fine particles are dispersed have been developed, and electrical contact materials having various surface treatments have been developed to improve the sliding characteristics of electrical contact materials.
例如本發明者等人於專利文獻1中提供有一種電氣接點材 料,該電氣接點材料係於導電性基體上設置有第1貴金屬層及第2貴金屬層,該第1貴金屬層由表面之算術平均粗糙度Ra=(A)μm、且(A)為0.05~0.5之貴金屬或以貴金屬作為主成分之合金所構成,該第2貴金屬係於該第1貴金屬層之上層由皮膜厚度為0.001×(A)μm以上且(A)μm以下之貴金屬或以貴金屬作為主成分之合金所構成,並且形成上述第1貴金屬層之貴金屬係選自金、銀、鈀及鉑,相對於形成上述第1貴金屬層之貴金屬或作為形成上述第1貴金屬層之合金之主成分之貴金屬,形成上述第2貴金屬層之貴金屬或作為形成上述第2貴金屬層之合金之主成分之貴金屬為不同之元素。該電氣接點材料係於滑動特性或耐摩耗性方面優異,長壽命,且可低成本地製造之電氣接點材料。 For example, the inventors of the present invention provide an electrical contact material in Patent Document 1. The electrical contact material is provided with a first noble metal layer and a second noble metal layer on the conductive substrate. The first noble metal layer has an arithmetic mean roughness Ra of the surface (=A) μm and (A) is 0.05. a precious metal of ~0.5 or an alloy containing a noble metal as a main component, and the second noble metal is a noble metal or a noble metal having a film thickness of 0.001 × (A) μm or more and (A) μm or less in the upper layer of the first noble metal layer. The noble metal forming the first noble metal layer is selected from the group consisting of gold, silver, palladium, and platinum, and is a main component of the noble metal forming the first noble metal layer or the alloy forming the first noble metal layer. The noble metal of the component is a different element from the noble metal forming the second noble metal layer or the noble metal forming the main component of the alloy forming the second noble metal layer. The electrical contact material is an electrical contact material which is excellent in sliding characteristics or wear resistance, long in life, and can be manufactured at low cost.
[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]
[專利文獻1]日本專利第5128153號公報 [Patent Document 1] Japanese Patent No. 5128153
且說,根據專利文獻1之構成而製作電氣接點材料並進行評價,結果得知雖然可見輕負載下之滑動特性非常優異之效果,但若例如負載成為50gf以上,則可見滑動特性變差之傾向,又,有環境試驗後之耐蝕性變差之情形。得知於進行硫化氫(H2S)氣體或二氧化硫(SO2)氣體等之高負載環境下之試驗時,自上述第1貴金屬層與第2貴金屬層之2層貴金屬層之針孔(pinhole)或設置於上述第1貴金屬層與導電性基體之間之底層金屬層之針孔,形成源自底層金屬或基體之成分之腐蝕產物,而導致接觸電阻變差。 In addition, the electrical contact material was produced and evaluated according to the configuration of the patent document 1. As a result, it was found that the sliding property under the light load was excellent, but if the load was 50 gf or more, the sliding property was deteriorated. Moreover, there is a case where the corrosion resistance after the environmental test is deteriorated. It is known that when testing under high load conditions such as hydrogen sulfide (H 2 S) gas or sulfur dioxide (SO 2 ) gas, pinholes of two precious metal layers from the first noble metal layer and the second noble metal layer (pinhole) Or a pinhole provided in the underlying metal layer between the first noble metal layer and the conductive substrate to form a corrosion product derived from a component of the underlying metal or the substrate, resulting in deterioration of contact resistance.
本發明之課題在於提供一種電氣接點材料及其製造方法,該 電氣接點材料解決如上所述之問題,滑動負載為50gf以上,即便成為例如100gf左右之高負載亦顯示出優異之耐磨耗性,並且尤其是長時間暴露於大氣中之嚴酷環境下亦可使用,即便於例如H2S氣體或SO2氣體氛圍下等腐蝕環境下之加速試驗後,亦可大幅度地抑制電氣接點材料之接觸電阻上升,而長期可靠性較高。 An object of the present invention is to provide an electrical contact material which solves the above problems and has a sliding load of 50 gf or more, and exhibits excellent wear resistance even at a high load of, for example, about 100 gf. It can also be used in harsh environments, especially in the harsh environment exposed to the atmosphere for a long time. Even after the accelerated test in a corrosive environment such as H 2 S gas or SO 2 gas atmosphere, the electrical contact can be greatly suppressed. The contact resistance of the material rises and the long-term reliability is high.
本發明者等人對於上述課題進行努力研究開發,結果發現:針對設置於導電性基體上之第1貴金屬層與第2貴金屬層之各金屬層,適當地調整其表面粗糙度、層之厚度、層之硬度等,藉此可提供一種不僅高負載下之耐摩耗性或滑動特性優異,且耐蝕性亦優異之電氣接點材料。本發明係基於該見解而完成者。 As a result of intensive research and development of the above-mentioned problems, the present inventors have found that the surface roughness and the thickness of the layer are appropriately adjusted for each of the first noble metal layer and the second noble metal layer provided on the conductive substrate. The hardness of the layer or the like can provide an electrical contact material which is excellent not only in abrasion resistance or sliding property under high load but also in excellent corrosion resistance. The present invention has been completed based on this finding.
即,根據本發明,可提供以下之手段。 That is, according to the present invention, the following means can be provided.
(1)一種電氣接點材料,其係於導電性基體之表面上具有第1貴金屬層,且於上述第1貴金屬層之表面上具有第2貴金屬層者,其特徵在於:上述第1貴金屬層之表面之算術平均粗糙度Ra=A μm為A<1,且該第1貴金屬層之硬度Hv為150以上,並且上述第2貴金屬層之厚度超過A μm且為1μm以下,且該第2貴金屬層之表面之算術平均粗糙度Ra=B μm為B≦0.1。 (1) An electrical contact material having a first noble metal layer on a surface of a conductive substrate and a second noble metal layer on a surface of the first noble metal layer, wherein the first noble metal layer The arithmetic mean roughness Ra of the surface is A<1, and the hardness Hv of the first noble metal layer is 150 or more, and the thickness of the second noble metal layer exceeds A μm and is 1 μm or less, and the second noble metal The arithmetic mean roughness Ra = B μm of the surface of the layer is B ≦ 0.1.
(2)如(1)項之電氣接點材料,其中上述A之值為0.001以上且未達0.500。 (2) The electrical contact material of item (1), wherein the value of A above is 0.001 or more and less than 0.500.
(3)如(1)或(2)項之電氣接點材料,其中上述第1貴金屬層及第2貴金屬層分別由金、金合金、銀、銀合金、鉑、鉑合金、銦、銦合金、錫、錫合金、鈀、鈀合金、釕、釕合金、銠、銠合金、鋨、鋨合金、銥、銥合金中之任一種所構成。 (3) The electrical contact material of (1) or (2), wherein the first noble metal layer and the second precious metal layer are respectively gold, gold alloy, silver, silver alloy, platinum, platinum alloy, indium, indium alloy Any of tin, tin alloy, palladium, palladium alloy, niobium, tantalum alloy, niobium, niobium alloy, tantalum, niobium alloy, tantalum or niobium alloy.
(4)如(1)至(3)項中任一項之電氣接點材料,其中上述第1貴金 屬層由鈀、鈀合金、釕、釕合金、銠、銠合金、鋨、鋨合金、銥、銥合金中之任一種所構成。 (4) The electrical contact material of any one of (1) to (3), wherein the first precious gold is The genus layer is composed of any one of palladium, palladium alloy, ruthenium, iridium alloy, ruthenium, osmium alloy, ruthenium, osmium alloy, ruthenium or osmium alloy.
(5)如(1)至(4)項中任一項之電氣接點材料,其中上述第2貴金屬層由金、金合金、銀、銀合金、鉑、鉑合金、銦、銦合金、錫、錫合金中之任一種所構成。 (5) The electrical contact material of any one of (1) to (4), wherein the second noble metal layer is made of gold, gold alloy, silver, silver alloy, platinum, platinum alloy, indium, indium alloy, tin And any of the tin alloys.
(6)如(1)至(5)項中任一項之電氣接點材料,其中上述導電性基體與上述第1貴金屬層之間至少具有1層底層金屬層。 (6) The electrical contact material according to any one of (1) to (5), wherein the conductive substrate and the first noble metal layer have at least one underlying metal layer.
(7)如(6)項之電氣接點材料,其中上述底層金屬層由鎳、鎳合金、鈷、鈷合金中之任一種所構成。 (7) The electrical contact material of (6), wherein the underlying metal layer is composed of any one of nickel, a nickel alloy, cobalt, and a cobalt alloy.
(8)如(6)或(7)項之電氣接點材料,其中上述底層金屬層之厚度為0.05~3.00μm。 (8) The electrical contact material of item (6) or (7), wherein the thickness of the underlying metal layer is 0.05 to 3.00 μm.
(9)如(1)至(8)項中任一項之電氣接點材料,其中上述導電性基體由銅、銅合金、鐵、鐵合金、鋁、鋁合金中之任一種所構成。 (9) The electrical contact material according to any one of (1) to (8), wherein the conductive substrate is made of any one of copper, a copper alloy, iron, an iron alloy, aluminum, and an aluminum alloy.
(10)如(1)至(9)項中任一項之電氣接點材料,其中上述導電性基體之母相之平均結晶粒徑為5μm以下。 (10) The electrical contact material according to any one of (1) to (9) wherein the parent phase of the conductive substrate has an average crystal grain size of 5 μm or less.
(11)一種如(1)至(10)項中任一項之電氣接點材料之製造方法,其特徵在於:利用電鍍法設置上述第1貴金屬層及第2貴金屬層之至少一層。 (11) A method of producing an electrical contact material according to any one of (1) to (10), wherein at least one of the first noble metal layer and the second noble metal layer is provided by a plating method.
此處,於本發明中,上述第1貴金屬層或第2貴金屬層中之所謂「貴金屬」,係指較導電性基體之材料貴重之金屬。 Here, in the present invention, the term "precious metal" in the first noble metal layer or the second noble metal layer means a metal which is more expensive than the material of the conductive substrate.
根據本發明,可提供一種顯示出高負載下之耐磨耗性或滑動特性、及耐蝕性,並且進而接觸電阻較小之電氣接點材料。又,本發明之電氣接點材料雖然較例如專利文獻1中記載者等更厚地鍍敷,但有最表面之色調不易劣化、外觀長期良好之效果。 According to the present invention, it is possible to provide an electrical contact material which exhibits wear resistance or sliding characteristics under high load, and corrosion resistance, and further has small contact resistance. In addition, the electrical contact material of the present invention is plated thicker than that described in, for example, Patent Document 1, but has an effect that the color of the outermost surface is not easily deteriorated and the appearance is good for a long period of time.
本發明之上述及其他特徵及優勢可適宜參照隨附之圖式,基 於下述記載而更明確。 The above and other features and advantages of the present invention can be suitably referred to the accompanying drawings. It is more clear from the following description.
1‧‧‧導電性基體 1‧‧‧Electrically conductive substrate
2‧‧‧第1貴金屬層 2‧‧‧1st precious metal layer
3‧‧‧第2貴金屬層 3‧‧‧2nd precious metal layer
4‧‧‧底層金屬層 4‧‧‧Underlying metal layer
圖1係示意地表示本發明之一實施態樣之剖面圖。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view schematically showing an embodiment of the present invention.
圖2係示意地表示本發明之另一實施態樣之剖面圖。 Fig. 2 is a cross-sectional view schematically showing another embodiment of the present invention.
圖3係示意地表示本發明之又一實施態樣之剖面圖。 Fig. 3 is a cross-sectional view schematically showing still another embodiment of the present invention.
圖4係示意地表示本發明之一實施態樣之第1貴金屬層與第2貴金屬層之邊界的部分放大剖面圖。 Fig. 4 is a partially enlarged cross-sectional view schematically showing a boundary between a first noble metal layer and a second noble metal layer according to an embodiment of the present invention.
圖5係示意地表示本發明之另一實施態樣之第1貴金屬層與第2貴金屬層之邊界的部分放大剖面圖。 Fig. 5 is a partially enlarged cross-sectional view schematically showing a boundary between a first noble metal layer and a second noble metal layer according to another embodiment of the present invention.
本發明之電氣接點材料係於導電性基體之表面上具有第1貴金屬層,且於上述第1貴金屬層之表面上具有第2貴金屬層者,並且上述第1貴金屬層之表面之算術平均粗糙度Ra=(A)μm為(A)<1,且該第1貴金屬層之硬度Hv為150以上,上述第2貴金屬層之厚度為超過(A)μm且為1μm以下,且該第2貴金屬層之表面之算術平均粗糙度Ra=(B)μm為(B)≦0.1。此處,所謂算術平均粗糙度Ra,係指依據JIS B 0601:2013之算術平均粗糙度Ra。 The electrical contact material of the present invention has a first noble metal layer on the surface of the conductive substrate, and has a second noble metal layer on the surface of the first noble metal layer, and the arithmetic mean roughness of the surface of the first noble metal layer Degree Ra = (A) μm is (A) < 1, and the hardness Hv of the first noble metal layer is 150 or more, and the thickness of the second noble metal layer is more than (A) μm and 1 μm or less, and the second noble metal The arithmetic mean roughness Ra = (B) μm of the surface of the layer is (B) ≦ 0.1. Here, the arithmetic mean roughness Ra means an arithmetic mean roughness Ra in accordance with JIS B 0601:2013.
再者,於本發明中,第1貴金屬層與第2貴金屬層之各自係其成分(即,貴金屬元素之種類)相互不同之層。第1貴金屬層與第2貴金屬層之各自可由單一之貴金屬種類所構成,亦可由包含貴金屬之合金所構成。於由包含貴金屬之合金所構成之情形時,該層中之質量比最大之元素種類必須為貴金屬。若於1個貴金屬層由包含複數種貴金屬之合金所構成之情形時,該層中之全部貴金屬之合計之質量比於該層中需成為最大比 率。其中,於貴金屬之合金之比率恰好為50%時,亦將其視為貴金屬層。 Furthermore, in the present invention, each of the first noble metal layer and the second noble metal layer is a layer in which components (that is, types of noble metal elements) are different from each other. Each of the first noble metal layer and the second noble metal layer may be composed of a single noble metal species or may be composed of an alloy containing a noble metal. In the case of an alloy composed of a noble metal, the element type having the largest mass ratio in the layer must be a noble metal. In the case where a noble metal layer is composed of an alloy containing a plurality of noble metals, the total mass of all the precious metals in the layer is greater than the ratio in the layer to be the maximum ratio. rate. Among them, when the ratio of the alloy of the precious metal is exactly 50%, it is also regarded as a precious metal layer.
此處,於第1貴金屬層與第2貴金屬層分別由單一之貴金屬種所構成之情形時,該貴金屬元素種類需相互不同。另一方面,於第1貴金屬層與第2貴金屬層分別由包含貴金屬之合金所構成之情形時,構成該合金層之上述層中之質量比最大之貴金屬元素種類需相互不同。 Here, when the first noble metal layer and the second noble metal layer are each composed of a single noble metal species, the noble metal element types need to be different from each other. On the other hand, when the first noble metal layer and the second noble metal layer are each composed of an alloy containing a noble metal, the types of noble metal elements having the largest mass ratio among the layers constituting the alloy layer need to be different from each other.
使用圖式說明本發明之電氣接點材料。 The electrical contact material of the present invention will be described using the drawings.
圖1係示意地表示本發明之一實施態樣之剖面圖。於該實施態樣中,於導電性基體1之表面上設置第1貴金屬層2,進而於該表面上設置第2貴金屬層3。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view schematically showing an embodiment of the present invention. In this embodiment, the first noble metal layer 2 is provided on the surface of the conductive substrate 1, and the second noble metal layer 3 is further provided on the surface.
圖2係示意地表示本發明之另一實施態樣之剖面圖。此處,於導電性基體1之表面上,設置由第1貴金屬層2及第2貴金屬層3所構成之被覆層之底層金屬層4。 Fig. 2 is a cross-sectional view schematically showing another embodiment of the present invention. Here, the underlying metal layer 4 of the coating layer composed of the first noble metal layer 2 and the second noble metal layer 3 is provided on the surface of the conductive substrate 1.
圖3係示意地表示本發明之又一實施態樣之剖面圖。此處,於導電性基體1之表面上設置有底層金屬層4,於底層金屬層4上局部地設置有由第1貴金屬層2及第2貴金屬層3所構成之被覆層,而謀求省貴金屬化之成本降低(cost down)。再者,關於圖3,導電性基體1上之底層金屬層4可局部地設置,亦可僅設置於例如設置由第1貴金屬層2及第2貴金屬層3所構成之被覆層之部位(與被覆層之形狀一致)。 Fig. 3 is a cross-sectional view schematically showing still another embodiment of the present invention. Here, the underlying metal layer 4 is provided on the surface of the conductive substrate 1, and the coating layer composed of the first noble metal layer 2 and the second noble metal layer 3 is partially provided on the underlying metal layer 4 to save precious metals. Cost reduction. Further, in FIG. 3, the underlying metal layer 4 on the conductive substrate 1 may be partially provided, or may be provided only at a portion where the coating layer composed of the first noble metal layer 2 and the second noble metal layer 3 is provided (for The shape of the coating is the same).
於圖1~圖3中,簡化地藉由直線表示第1貴金屬層2與第2貴金屬層3之邊界,實際上,如於圖4之部分放大剖面圖中示意地表示般,導電性基體1之表面上之第1貴金屬層2之表面具有如算術平均粗糙度Ra=(A)μm之凹凸,第2貴金屬層3之膜厚係形成為超過(A)μm且為1μm以下。 In FIGS. 1 to 3, the boundary between the first noble metal layer 2 and the second noble metal layer 3 is shown by a straight line in a simplified manner. Actually, as shown schematically in a partially enlarged cross-sectional view of FIG. 4, the conductive substrate 1 is schematically shown. The surface of the first noble metal layer 2 on the surface has irregularities such as arithmetic mean roughness Ra = (A) μm, and the thickness of the second noble metal layer 3 is formed to exceed (A) μm and is 1 μm or less.
再者,於如圖5之部分放大剖面圖中示意地表示般對第2貴金屬層3使用例如光澤鍍敷之情形等時,亦可於第1貴金屬層2之表面側之凹部較 厚地設置第2貴金屬層3,且於凸部較薄地設置第2貴金屬層3。又,此時例如亦可於鍍敷後將表面輕輕地磨削而削薄,僅於第1貴金屬層2之表面側之凹部被覆第2貴金屬層3。此處,將第2貴金屬層3較厚地設置於第1貴金屬層2之表面側之凹部、較薄地設置於凸部之情形時之第2貴金屬層3之膜厚係定義為算術平均值。 In the case where the second noble metal layer 3 is used, for example, in the case of gloss plating, as shown in the enlarged cross-sectional view of FIG. 5, the concave portion on the surface side of the first noble metal layer 2 may be used. The second noble metal layer 3 is thickly provided, and the second noble metal layer 3 is provided thinly at the convex portion. Moreover, at this time, for example, the surface may be lightly ground and thinned after plating, and the second noble metal layer 3 may be covered only in the concave portion on the surface side of the first noble metal layer 2. Here, the film thickness of the second noble metal layer 3 when the second noble metal layer 3 is thickly provided on the surface of the first noble metal layer 2 and the thin portion is provided in the convex portion is defined as an arithmetic mean value.
又,作為所使用之導電性基體,較佳為銅或銅合金、鐵或鐵合金、鋁或鋁合金製之導電性基體,其中較佳為導電率良好之銅或銅合金製之導電性基體。 Further, as the conductive substrate to be used, a conductive substrate made of copper or a copper alloy, iron or an iron alloy, aluminum or an aluminum alloy is preferable, and among them, a conductive substrate made of copper or a copper alloy having a good electrical conductivity is preferable.
例如作為銅合金之例,可使用:作為CDA(Copper Development Association,銅業發展協會)所揭示合金之「C14410(Cu-0.15Sn,古河電氣工業(股份)製造,商品名:EFTEC-3)」、「C19400(Cu-Fe系合金材料,Cu-2.3Fe-0.03P-0.15Zn)、「C18045(Cu-0.3Cr-0.25Sn-0.5Zn,古河電氣工業(股份)製造,商品名:EFTEC-64T)」、「C26800(Cu-35%Zn)」、及「C71500(Cu-30%Ni)」等。再者,各元素前之數字之單位為質量%。該等銅合金製之導電性基體由於各自導電率或強度不同,故而可適宜根據要求特性而選擇使用,就可提高導電性或散熱性之觀點而言,較佳為製成導電率為5%IACS(International Annealed Copper Standard,國際退火銅標準)以上之銅合金之條材。再者,將銅或銅合金製成導電性基體時之所謂「基體成分」係表示銅。 For example, as an example of a copper alloy, "C14410 (Cu-0.15Sn, manufactured by Furukawa Electric Co., Ltd., trade name: EFTEC-3)" which is an alloy disclosed by the CDA (Copper Development Association). "C19400 (Cu-Fe alloy material, Cu-2.3Fe-0.03P-0.15Zn), "C18045 (Cu-0.3Cr-0.25Sn-0.5Zn, manufactured by Furukawa Electric Co., Ltd., trade name: EFTEC- 64T)", "C26800 (Cu-35%Zn)", and "C71500 (Cu-30%Ni)". Furthermore, the unit of the number before each element is mass%. Since the conductive substrates made of these copper alloys have different conductivity or strength, they can be selected and used according to the required characteristics, and from the viewpoint of improving conductivity or heat dissipation, the conductivity is preferably 5%. Bars of copper alloys above IACS (International Annealed Copper Standard). Further, the term "base component" when copper or a copper alloy is used as a conductive substrate means copper.
又,作為鐵或鐵合金,例如可使用:42合金(Fe-42 mass%Ni)或不鏽鋼(stainless)等。此時所謂基體成分係表示鐵。 Further, as the iron or the iron alloy, for example, a 42 alloy (Fe-42 mass% Ni) or stainless steel (stainless) or the like can be used. At this time, the matrix component means iron.
關於導電性基體之厚度,並無特別限制,通常為0.05~2.00mm,較佳為0.10~1.00mm。 The thickness of the conductive substrate is not particularly limited, but is usually 0.05 to 2.00 mm, preferably 0.10 to 1.00 mm.
進而,作為本發明中之導電性基體,藉由採用導電性基體母材(matrix)之平均結晶粒徑為5μm以下者,而可使析出於其上層之鍍層成為緻密之析出,結果可形成具有多數晶粒之鍍層而使晶界擴散分散,從 而大幅度地延遲基體成分之擴散到達表層之時間。其結果為,可提供可抑制已擴散至第2貴金屬層之表層中的基體成分之腐蝕、抑制接觸電阻之上升而可靠性較高之電氣接點材料。又,亦可獲得導電性基體母材之平均結晶粒徑越小,導電性基體之彎曲加工性越優異之相乘效果。 Further, as the conductive substrate in the present invention, by using a conductive matrix base material having an average crystal grain size of 5 μm or less, the plating layer deposited on the upper layer can be densely precipitated, and as a result, it can be formed. The coating of most grains causes the grain boundary to diffuse and diffuse, The time during which the diffusion of the matrix component reaches the surface layer is greatly delayed. As a result, it is possible to provide an electrical contact material which is capable of suppressing corrosion of a matrix component which has diffused into the surface layer of the second noble metal layer and suppressing an increase in contact resistance and having high reliability. Further, the smaller the average crystal grain size of the conductive base material, the more excellent the bending workability of the conductive substrate.
導電性基體母材之平均結晶粒徑較佳為5μm以下,為了更進一步提高鍍敷之緻密性,更佳為3μm以下,進而較佳為1μm以下。其下限值並無特別限制,通常為0.001μm以上。 The average crystal grain size of the conductive base material is preferably 5 μm or less, and more preferably 3 μm or less, and still more preferably 1 μm or less in order to further improve the density of plating. The lower limit thereof is not particularly limited, and is usually 0.001 μm or more.
於本發明中,作為形成第1貴金屬層及第2貴金屬層之金屬或其合金之例,可列舉:金、金合金、銀、銀合金、鉑、鉑合金、銦、銦合金、錫、錫合金、鈀、鈀合金、釕、釕合金、銠、銠合金、鋨、鋨合金、銥、銥合金等。 In the present invention, examples of the metal forming the first noble metal layer and the second noble metal layer or an alloy thereof include gold, gold alloy, silver, silver alloy, platinum, platinum alloy, indium, indium alloy, tin, and tin. Alloys, palladium, palladium alloys, niobium, tantalum alloys, niobium, niobium alloys, tantalum, niobium alloys, tantalum, niobium alloys, etc.
此處,第1貴金屬層之作用係提高最表面所形成之第2貴金屬層之耐磨耗性,進而提高耐蝕性。其原因在於:藉由將第1貴金屬層表面之算術平均粗糙度Ra=(A)μm設為(A)<1,可提高耐磨耗性,且藉由將其硬度Hv設為150以上,較佳為設為200以上,可更進一步改善耐磨耗性。 Here, the function of the first noble metal layer is to improve the wear resistance of the second noble metal layer formed on the outermost surface, thereby improving the corrosion resistance. The reason for this is that the abrasion resistance can be improved by setting the arithmetic mean roughness Ra = (A) μm of the surface of the first noble metal layer to (A) < 1, and the hardness Hv is set to 150 or more. It is preferable to set it as 200 or more, and the abrasion resistance can be further improved.
又,較佳為將上述(A)之值設為0.001以上且未達0.500,藉此可獲得耐蝕性更優異之電氣接點材料。 Further, it is preferable that the value of the above (A) is 0.001 or more and less than 0.500, whereby an electrical contact material having more excellent corrosion resistance can be obtained.
尤其是為了易於達成此種耐磨耗性與耐蝕性之提高,作為第1貴金屬層,較佳為由鈀、鈀合金、釕、釕合金、銠、銠合金、鋨、鋨合金、銥、銥合金中之任一種所構成,進而較佳為第1貴金屬層由鈀、鈀合金、銠、銠合金中之任一種所構成,原因在於可進一步減小耐磨耗性及接觸電阻。(A)之值較佳為0.001以上且未達0.5,進而較佳為0.005~0.1。藉由將(A)之值設為該範圍,可使其後形成於第1貴金屬層上之第2貴金屬層之表面成為易變得平滑者。 In particular, in order to easily achieve such improvement in abrasion resistance and corrosion resistance, the first noble metal layer is preferably made of palladium, palladium alloy, ruthenium, iridium alloy, ruthenium, osmium alloy, ruthenium, osmium alloy, ruthenium or osmium. It is preferable that the first noble metal layer is composed of any one of the alloys, and is preferably made of any one of palladium, a palladium alloy, a ruthenium, and a ruthenium alloy because the wear resistance and the contact resistance can be further reduced. The value of (A) is preferably 0.001 or more and less than 0.5, and more preferably 0.005 to 0.1. By setting the value of (A) to this range, the surface of the second noble metal layer formed on the first noble metal layer can be easily smoothed.
再者,對於該第1貴金屬層之被覆厚度,並無特別限制,若考慮成本 或彎曲加工性,則較佳為0.001~3μm,進而較佳為0.05~1μm。 Furthermore, the thickness of the coating of the first precious metal layer is not particularly limited, and the cost is considered. Or the bending workability is preferably 0.001 to 3 μm, more preferably 0.05 to 1 μm.
第2貴金屬層係由與構成第1貴金屬層之貴金屬不同之貴金屬所構成。第2貴金屬層係本發明之電氣接點材料之最表面被覆層,第2貴金屬層之皮膜厚度為超過作為第1貴金屬層之表面之算術平均粗糙度(Ra)之(A)μm且為1μm以下,且該第2貴金屬層之表面之算術平均粗糙度Ra=(B)μm且B≦0.1。該第2貴金屬層係作為保護第1貴金屬層且與導電特性良好之第1貴金屬層不同之貴金屬層而設置者。第2貴金屬層之表面成為初期之滑動面,藉由於作為第1貴金屬層表面之算術平均粗糙度(Ra)的(A)μm之凹凸中埋設第2貴金屬層,而作為兼具作為電氣接點材料所需之低接觸電阻特性或作為滑動接點所需之功能之表面潤滑性、耐摩耗性之被覆層發揮功能。第2貴金屬層不僅以填埋第1貴金屬層之凹凸之程度存在,且藉由將其厚度設為超過上述(A)μm且為1μm以下,可製成更進一步提高耐蝕性之皮膜。進而,藉由將第2貴金屬層表面之算術平均粗糙度Ra=(B)μm設為(B)≦0.1,而發揮抑制由凹凸所致之磨耗,而防止第1貴金屬層甚至是導電性基體暴露之效果。於如此將第2貴金屬層設為厚於第1貴金屬層之算術平均粗糙度(Ra)=(A)μm之本發明之電氣接點材料中,由於構成被覆層之貴金屬之使用量多於專利文獻1,故而變得成本高,但由於就耐蝕性提高之觀點而言較為優異,故而可使長期使用環境下之總成本(total cost)降低。 The second noble metal layer is composed of a noble metal different from the noble metal constituting the first noble metal layer. The second noble metal layer is the outermost coating layer of the electrical contact material of the present invention, and the film thickness of the second noble metal layer is (A) μm and is 1 μm exceeding the arithmetic mean roughness (Ra) of the surface of the first noble metal layer. Hereinafter, the arithmetic mean roughness Ra of the surface of the second noble metal layer is (B) μm and B ≦ 0.1. The second noble metal layer is provided as a noble metal layer different from the first noble metal layer which protects the first noble metal layer and has good conductivity. The surface of the second noble metal layer is an initial sliding surface, and the second precious metal layer is embedded in the unevenness of (A) μm which is the arithmetic mean roughness (Ra) of the surface of the first noble metal layer, and serves as an electrical contact. The low contact resistance characteristics required for the material or the surface lubricity and abrasion resistance of the function required for the sliding contact function. The second noble metal layer is not only filled with the unevenness of the first noble metal layer, but also has a thickness of more than the above (A) μm and 1 μm or less, whereby a film having further improved corrosion resistance can be obtained. Further, by setting the arithmetic mean roughness Ra = (B) μm of the surface of the second noble metal layer to (B) ≦ 0.1, it is possible to suppress the abrasion caused by the unevenness, thereby preventing the first noble metal layer or even the conductive substrate. The effect of exposure. In the electrical contact material of the present invention in which the second noble metal layer is thicker than the arithmetic mean roughness (Ra) of the first noble metal layer (A) μm, the amount of the precious metal constituting the coating layer is more than the patent. Document 1 is expensive, but it is excellent in terms of improvement in corrosion resistance, so that the total cost in a long-term use environment can be lowered.
作為上述第2貴金屬層之材料,可適宜地使用金、金合金、銀、銀合金、鉑、鉑合金、銦、銦合金、錫、錫合金等,尤其於要求耐蝕性之用途中,較佳為金、金合金、鉑、鉑合金。另一方面,若為電氣接點經樹脂鑄模而暴露於大氣中之顧慮較少之電氣接點材料,則亦可使用銀、銀合金、銦、銦合金、錫、錫合金作為第2貴金屬層之材料。該等金屬或其合金由於顯示出優異之焊料潤濕性或接觸電阻特性,故而可根據用途或 實例而適宜選擇。 As the material of the second noble metal layer, gold, a gold alloy, silver, a silver alloy, platinum, a platinum alloy, indium, an indium alloy, tin, a tin alloy or the like can be suitably used, and in particular, in applications requiring corrosion resistance, it is preferred. It is gold, gold alloy, platinum, platinum alloy. On the other hand, if the electrical contact is exposed to the resin and the electrical contact material is less likely to be exposed to the atmosphere, silver, silver alloy, indium, indium alloy, tin, tin alloy may be used as the second precious metal layer. Material. These metals or alloys thereof may exhibit excellent solder wettability or contact resistance characteristics, and may be used depending on the use or Examples are suitable for selection.
於本發明之電氣接點材料(例如滑動接點材料)中,可於導電性基體與第1貴金屬層之間設置底層金屬層,亦可不設置。藉由設置由例如鎳、鎳合金、鈷、鈷合金中之任一種所構成之底層金屬層,可提高第1貴金屬層與基體成分之擴散阻礙或密接性,故而較佳。尤其於藉由鍍敷處理將比導電性基體更貴之金屬作為上述第1貴金屬層或第2貴金屬層而形成之本發明中,為了提高密接性或防止置換,有效的是於該鍍敷處理前藉由閃(flash)鍍或觸擊(strike)鍍敷等基底處理而設置底層金屬層之方法。又,底層金屬層亦可製成複數層,可根據上述第1貴金屬層或第2貴金屬層之被覆之規格或用途等,藉由常法而做成為各種構成。作成單一層或複數層之底層金屬層之合計厚度較佳為0.05~3μm,更佳為0.5~1μm。 In the electrical contact material (for example, a sliding contact material) of the present invention, an underlying metal layer may be provided between the conductive substrate and the first noble metal layer, or may not be provided. It is preferable to provide an underlying metal layer composed of, for example, any one of nickel, a nickel alloy, cobalt, and a cobalt alloy to improve diffusion barrier or adhesion between the first noble metal layer and the matrix component. In particular, in the present invention in which a metal which is more expensive than a conductive substrate is formed as the first noble metal layer or the second noble metal layer by a plating treatment, in order to improve adhesion or prevent displacement, it is effective before the plating treatment. A method of providing an underlying metal layer by substrate processing such as flash plating or strike plating. Further, the underlying metal layer may be formed into a plurality of layers, and various structures may be formed by a usual method depending on the specifications or use of the first noble metal layer or the second noble metal layer. The total thickness of the underlying metal layer formed as a single layer or a plurality of layers is preferably 0.05 to 3 μm, more preferably 0.5 to 1 μm.
為了製造本發明之電氣接點材料,可利用:鍍敷、鍍層(clad)、蒸鍍、濺鍍(spatter)等各種皮膜形成法,作為尤其易於形成薄膜之方法,較佳為利用電鍍法設置第1貴金屬層及第2貴金屬層之至少一層,更佳為利用電鍍法形成第1貴金屬層及第2貴金屬層之兩層。電鍍液之組成及鍍敷條件可根據常法而適宜決定。又,為了抑制所需金屬量,將第1貴金屬層或第2貴金屬層、或其兩者之貴金屬被覆層局部地設為條狀或點狀等亦有用。 In order to manufacture the electrical contact material of the present invention, various film formation methods such as plating, plating, vapor deposition, and sputtering can be used, and as a method of forming a film particularly, it is preferable to use a plating method. It is more preferable to form at least one of the first noble metal layer and the second noble metal layer by electroplating to form two layers of the first noble metal layer and the second noble metal layer. The composition of the plating solution and the plating conditions can be appropriately determined according to the usual method. Further, in order to suppress the amount of metal required, it is also useful to partially form the noble metal layer of the first noble metal layer or the second noble metal layer or both of them as a strip or a dot.
關於本發明之電氣接點材料中之由上述第1貴金屬層與第2貴金屬層所構成之被覆層,尤其是無論光澤、半光澤、無光澤之外觀種類如何均可應用。又,即便僅製成上述本發明之構成,效果亦充分,進而為了提高效果,亦較佳為採用使通常所使用之各種添加劑、分散劑、分散粒子等含有於由上述第1貴金屬層與第2貴金屬層所構成之被覆層之中間層內之1個以上之層中而成之複合被覆。 In the electrical contact material of the present invention, the coating layer composed of the first noble metal layer and the second noble metal layer can be applied in particular regardless of the type of appearance of gloss, semi-gloss, and matte. Further, even if only the configuration of the present invention described above is carried out, the effect is sufficient, and in order to improve the effect, it is preferable to use various additives, dispersants, dispersed particles, and the like which are generally used in the first noble metal layer and the first (2) Composite coating of one or more layers in the intermediate layer of the coating layer composed of the noble metal layer.
[實施例] [Examples]
以下,基於實施例更詳細地說明本發明,但本發明並不限定於該等。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
(實施例1) (Example 1)
對厚度0.3mm、寬度50mm之表1所示之導電性基體進行以下所示之前處理後,將表1所示之底層金屬層、第1貴金屬層、第2貴金屬層依序藉由電鍍法設置於導電性基體上,而獲得表1所示之發明例、比較例及先前例之電氣接點材料。 The conductive substrate shown in Table 1 having a thickness of 0.3 mm and a width of 50 mm was subjected to the following treatment, and the underlying metal layer, the first noble metal layer, and the second noble metal layer shown in Table 1 were sequentially set by electroplating. The electrical contact materials of the inventive examples, comparative examples, and prior examples shown in Table 1 were obtained on a conductive substrate.
再者,各層之被覆厚度係藉由使用螢光X射線膜厚測定裝置(SFT-9400,商品名,SII公司製造),將準直器(collimator)直徑設為0.5mm並對任意之部位測定10點,算出其平均值,設為被覆厚度。 In addition, the thickness of the coating layer of each layer was measured by using a fluorescent X-ray film thickness measuring device (SFT-9400, trade name, manufactured by SII Corporation), and the diameter of the collimator was set to 0.5 mm. At 10 o'clock, the average value is calculated and set as the coating thickness.
(前處理條件) (pre-processing conditions)
[陰極電解脫脂] [Cathode Electrolytic Degreasing]
脫脂液:NaOH 60g/l Degreasing liquid: NaOH 60g/l
脫脂條件:2.5A/dm2、溫度60℃、脫脂時間60秒 Degreasing conditions: 2.5A/dm 2 , temperature 60 ° C, degreasing time 60 seconds
[酸洗] [pickling]
酸洗液:10%硫酸 Pickling solution: 10% sulfuric acid
酸洗條件:30秒浸漬、室溫 Pickling conditions: 30 seconds impregnation, room temperature
(底層金屬層鍍敷條件) (underlying metal layer plating conditions)
[Ni鍍敷] [Ni plating]
鍍敷液:Ni(SO3NH2)2.4H2O 500g/l、NiCl2 30g/l、H3BO3 30g/l Plating solution: Ni(SO 3 NH 2 ) 2 . 4H 2 O 500g/l, NiCl 2 30g/l, H 3 BO 3 30g/l
鍍敷條件:溫度50℃ Plating conditions: temperature 50 ° C
[Co鍍敷] [Co plating]
鍍敷液:Co(SO3NH2)2.4H2O 500g/l、CoCl2 30g/l、H3BO3 30g/l Plating solution: Co(SO 3 NH 2 ) 2 . 4H 2 O 500g/l, CoCl 2 30g/l, H 3 BO 3 30g/l
鍍敷條件:溫度50℃ Plating conditions: temperature 50 ° C
(第1貴金屬層鍍敷條件) (1st precious metal layer plating condition)
[Pd鍍敷1(Pd1)] [Pd plating 1 (Pd1)]
鍍敷液:Pd(NH3)2Cl2 45g/l、NH4OH 90ml/l、(NH4)2SO4 50g/l、Parasigma光澤劑(商品名,松田產業股份有限公司製造)10ml/l Plating solution: Pd(NH 3 ) 2 Cl 2 45 g/l, NH 4 OH 90 ml/l, (NH 4 ) 2 SO 4 50 g/l, Parasigma Gloss (trade name, manufactured by Matsuda Industry Co., Ltd.) 10 ml/ l
鍍敷條件:電流密度5A/dm2、溫度60℃ Plating conditions: current density 5A/dm 2 , temperature 60 ° C
[Pd鍍敷2(Pd2)]無添加劑浴:於比較例2中使用 [Pd plating 2 (Pd2)] additive-free bath: used in Comparative Example 2
鍍敷液:Pd(NH3)2Cl2 45g/l、NH4OH 90ml/l、(NH4)2SO4 50g/l Plating solution: Pd(NH 3 ) 2 Cl 2 45g/l, NH 4 OH 90ml/l, (NH 4 ) 2 SO 4 50g/l
鍍敷條件:電流密度3A/dm2、溫度60℃ Plating conditions: current density 3A/dm 2 , temperature 60 ° C
[Rh鍍敷] [Rh plating]
鍍敷液:RHODEX(商品名,日本ELECTROPLATING ENGINEERS(股份)製造) Plating solution: RHODEX (trade name, manufactured by Japan ELECTROPLATING ENGINEERS (share))
鍍敷條件:1.3A/dm2、溫度50℃ Plating conditions: 1.3A/dm 2 , temperature 50°C
[Ru鍍敷] [Ru plating]
鍍敷液:RUTHENEX 100(商品名,日本ELECTROPLATING ENGINEERS(股份)製造) Plating solution: RUTHENEX 100 (trade name, manufactured by Japan ELECTROPLATING ENGINEERS (share))
鍍敷條件:電流密度1A/dm2、溫度65℃ Plating conditions: current density 1A/dm 2 , temperature 65°C
[Ir鍍敷] [Ir plating]
鍍敷液:IRIDEX 100(商品名,日本ELECTROPLATING ENGINEERS(股份)製造) Plating solution: IRIDEX 100 (trade name, manufactured by Japan ELECTROPLATING ENGINEERS (share))
鍍敷條件:0.2A/dm2、溫度85℃ Plating conditions: 0.2A/dm 2 , temperature 85°C
(第2貴金屬層鍍敷條件) (2nd precious metal layer plating conditions)
[Au鍍敷] [Au plating]
鍍敷液:KAu(CN)2 14.6g/l、C6H8O7 150g/l、K2C6H4O7 180g/l Plating solution: KAu(CN) 2 14.6g/l, C 6 H 8 O 7 150g/l, K 2 C 6 H 4 O 7 180g/l
鍍敷條件:溫度40℃ Plating conditions: temperature 40 ° C
[Pt鍍敷] [Pt plating]
鍍敷液:Pt(NO2)(NH3)2 10g/l、NaNO2 10g/l、NH4NO3 100g/l、NH3 50ml/l Plating solution: Pt(NO 2 )(NH 3 ) 2 10g/l, NaNO 2 10g/l, NH 4 NO 3 100g/l, NH 3 50ml/l
鍍敷條件:溫度80℃ Plating conditions: temperature 80 ° C
[Ag鍍敷] [Ag plating]
鍍敷液:AgCN 50g/l、KCN 100g/l、K2CO3 30g/l Plating solution: AgCN 50g/l, KCN 100g/l, K 2 CO 3 30g/l
鍍敷條件:電流密度1A/dm2、溫度30℃ Plating conditions: current density 1A/dm 2 , temperature 30 ° C
[Ag-Se合金鍍敷] [Ag-Se alloy plating]
鍍敷液:KCN 150g/l、K2CO3 15g/l、KAg[CN]2 75g/l、Na2O3Se-5H2O 5g/l Plating solution: KCN 150g/l, K 2 CO 3 15g/l, KAg[CN] 2 75g/l, Na 2 O 3 Se-5H 2 O 5g/l
鍍敷條件:電流密度2A/dm2、溫度50℃ Plating conditions: current density 2A/dm 2 , temperature 50 ° C
[Sn鍍敷] [Sn plating]
鍍敷液:SnSO4 80g/l、H2SO4 80g/l Plating solution: SnSO 4 80g/l, H 2 SO 4 80g/l
鍍敷條件:電流密度2A/dm2、溫度30℃ Plating conditions: current density 2A/dm 2 , temperature 30 ° C
針對所獲得之各電氣接點材料,利用以下之試驗條件對各種特性進行試驗、評價。將結果示於表2。 For each of the obtained electrical contact materials, various characteristics were tested and evaluated using the following test conditions. The results are shown in Table 2.
(1A)導電性基體之平均結晶粒徑(GS): (1A) Average crystal grain size (GS) of the conductive substrate:
藉由FIB(Focused Ion Beam,聚焦離子束)製作導電性基體之剖面試樣之3個視野後,進行SIM圖像觀察,針對每1視野之3個部位測定粒徑,將其平均值示於表1。 After three fields of the cross-sectional sample of the conductive substrate were produced by FIB (Focused Ion Beam), the SIM image was observed, and the particle size was measured for each of the three fields of view. The average value was shown in Table 1.
(1B)厚度測定:第1貴金屬層、第2貴金屬層、及底層金屬層之厚度係藉由SII NanoTechnology公司製造之螢光X射線膜厚計(商品名:SFT9400)進行測定。將準直器直徑設為0.5mm,對任意部位測定10點,算出其平均值,設為被覆厚度。將結果示於表1。 (1B) Thickness measurement: The thickness of the first noble metal layer, the second noble metal layer, and the underlying metal layer was measured by a fluorescent X-ray film thickness meter (trade name: SFT9400) manufactured by SII NanoTechnology Co., Ltd. The diameter of the collimator was set to 0.5 mm, and 10 points were measured for any portion, and the average value was calculated to be the coating thickness. The results are shown in Table 1.
(1C)硬度測定:依據JIS Z 2244:2009,測定將測定負載設為0.005N時之第1貴金屬層之維氏(Vickers)硬度(Hv)。再者,其係被覆第2貴金屬層前之硬度。將結果示於表1。 (1C) Hardness measurement: Vickers hardness (Hv) of the first noble metal layer when the measurement load was 0.005 N was measured in accordance with JIS Z 2244:2009. Furthermore, it is the hardness before coating the second precious metal layer. The results are shown in Table 1.
(1D)算術平均粗糙度Ra:算術平均粗糙度Ra係藉由小阪研究所股份有限公司製造之表面粗糙度計(商品名:Surfcorder SE3500)進 行測定。於觸針頂端半徑2μm、測定力0.75N以下之測定條件下,測定第1貴金屬層之算術平均粗糙度Ra=(A)μm與第2貴金屬層之算術平均粗糙度Ra=(B)μm。將結果示於表1。 (1D) Arithmetic Mean Roughness Ra: Arithmetic Mean Roughness Ra is obtained by a surface roughness meter (trade name: Surfcorder SE3500) manufactured by Kosaka Research Institute Co., Ltd. Line measurement. The arithmetic mean roughness Ra of the first noble metal layer (=A) μm and the arithmetic mean roughness Ra of the second noble metal layer (=B) μm were measured under the measurement conditions of the tip end radius of 2 μm and the measurement force of 0.75 N or less. The results are shown in Table 1.
(2A)動摩擦係數測定:使用滑動試驗裝置(HEIDON Type:14FW,商品名,新東科學公司製造)進行動摩擦係數測定。測定條件如下所述。R=2.0mm之鋼珠探針(probe)、滑動距離10mm、滑動速度100mm/分鐘、滑動次數往返100次、負載100gf (2A) Measurement of dynamic friction coefficient: The dynamic friction coefficient was measured using a sliding test apparatus (HEIDON Type: 14FW, trade name, manufactured by Shinto Scientific Co., Ltd.). The measurement conditions are as follows. R=2.0mm steel ball probe (probe), sliding distance 10mm, sliding speed 100mm/min, sliding times 100 times, load 100gf
於上述滑動試驗中,測定往返滑動次數為1次、50次、100次後之各動摩擦係數,並示於表2。 In the above sliding test, the dynamic friction coefficients of the number of round trips were measured once, 50 times, and 100 times, and are shown in Table 2.
(2B)磨耗深度:對於上述滑動試驗結束後之磨耗深度,使用顯微鏡(VH8000,商品名,KEYENCE公司製造),測定滑動痕中央剖面之深度(μm)。將其最深處作為磨耗深度示於表2。 (2B) Abrasion depth: The depth (μm) of the central section of the sliding mark was measured using a microscope (VH8000, trade name, manufactured by KEYENCE Co., Ltd.) for the abrasion depth after the end of the sliding test. The deepest portion is shown in Table 2 as the wear depth.
(2C)接觸電阻測定:如下所示測定接觸電阻作為耐蝕性之指標,並進行評價。於形成最表層(上述第2貴金屬層)後,藉由四端子法測定接觸電阻。測定係以最表層剛形成後(初期)、二氧化硫試驗(SO2 10ppm、40℃、80%RH、168小時)後、硫化氫試驗(H2S 3ppm、40℃、80%RH、168小時)後之3個水準進行。評價係使用半徑2mm之銀(Ag)探針,於10mA通電、負載10gf之條件下對測定點10點之接觸電阻進行測定,算出其平均值作為接觸電阻。作為評價,將10mΩ以下設為「優」並以「A」示於表2,將超過10mΩ且為50mΩ以下設為「良」並以「B」示於表2,將超過50mΩ且為100mΩ以下設為「可」並以「C」示於表2,將超過100mΩ者設為「不可」並以「D」示於表2。將實用等級判定為「C」或「B」或「A」。 (2C) Measurement of contact resistance: The contact resistance was measured as an index of corrosion resistance as shown below and evaluated. After the outermost layer (the second noble metal layer described above) was formed, the contact resistance was measured by a four-terminal method. The measurement was performed immediately after the formation of the outermost layer (initial), sulfur dioxide test (SO 2 10 ppm, 40 ° C, 80% RH, 168 hours), and hydrogen sulfide test (H 2 S 3 ppm, 40 ° C, 80% RH, 168 hours) The next three levels are carried out. The evaluation was carried out by using a silver (Ag) probe having a radius of 2 mm, measuring the contact resistance at 10 points of the measurement point under the condition of 10 mA energization and a load of 10 gf, and the average value was calculated as the contact resistance. In the evaluation, 10 mΩ or less is set to "excellent", and "A" is shown in Table 2, and more than 10 mΩ and 50 mΩ or less are set to "good", and "B" is shown in Table 2, and it is more than 50 mΩ and 100 mΩ or less. It is set to "OK" and is shown in Table 2 as "C", "Not" for those exceeding 100 mΩ and Table 2 as "D". The utility level is determined as "C" or "B" or "A".
(2D)彎曲加工性:針對各試樣,於彎曲加工半徑0.9mm(R/t=3)之條件下對壓延筋於直角方向上實施V彎曲試驗後,利用顯微鏡 (VH8000,商品名,KEYENCE公司製造)以觀察倍率200倍觀察其脊部。將未見裂痕者設為「優」並以「A」示於表2,將產生輕微裂痕者設為「可」並以「B」示於表2,將產生相對較大裂痕者設為「不可」並以「C」示於表2。將實用等級判定為「B」或「A」。 (2D) Bending workability: For each sample, a V bending test was performed on the rolling rib in a direction perpendicular to the bending radius of 0.9 mm (R/t = 3), and then the microscope was used. (VH8000, trade name, manufactured by KEYENCE Co., Ltd.) The ridge was observed at an observation magnification of 200 times. Those who have not seen cracks are set to "excellent" and are shown as "A" in Table 2. Those with slight cracks are set to "OK" and "B" are shown in Table 2, and those with relatively large cracks are set to " It is not possible and is shown in Table 2 with "C". The utility level is determined as "B" or "A".
(2E)焊料潤濕性:使用MODEL SAT-5100(商品名,Rhesca公司製造),將藉由上述鍍敷處理所獲得之各試驗片於Sn-3Ag-0.5Cu焊料浴中,於浴溫245℃、浸漬距離10mm、浸漬速度25mm/秒之條件下,浸漬於異丙醇25質量%松香焊劑(rosin flux)中。測定自浸漬試驗片至濕潤力過零為止之時間(zero cross time,過零時間)。將其結果之過零時間(秒)示於表2。將過零時間未達1秒者設為「優」,將1秒以上且3秒以內者設為「可」,將超過3秒者設為「不可」,評價焊料潤濕性。 (2E) Solder Wetting Property: Each test piece obtained by the above plating treatment was placed in a Sn-3Ag-0.5Cu solder bath at a bath temperature of 245 using MODEL SAT-5100 (trade name, manufactured by Rhesca). Under a condition of ° C, an immersion distance of 10 mm, and an immersion speed of 25 mm/sec, it was immersed in a rosin flux of 25 mass% of isopropyl alcohol. The time from the immersion test piece to the wetting force zero crossing (zero cross time) was measured. The zero-crossing time (seconds) of the results is shown in Table 2. When the zero-crossing time is less than one second, it is set to "excellent", and those of one second or longer and three seconds are set to "OK", and those that are more than three seconds are set to "not available", and the solder wettability is evaluated.
由上述結果得知,於各發明例中,即便於100gf之高滑動負載下亦顯示出穩定之動摩擦係數而滑動特性良好,對磨耗深度顯示出之耐磨耗性優異,接觸電阻所顯示出之耐蝕性優異,彎曲加工性與焊料潤濕性亦良好。 From the above results, in each of the inventions, even when the sliding load is high at 100 gf, a stable dynamic friction coefficient is exhibited, and the sliding property is good, and the wear resistance is excellent in the abrasion depth, and the contact resistance is shown. Excellent in corrosion resistance, and good in bending workability and solder wettability.
相對於此,於各比較例與先前例中,任一者之特性均為較差結果。 On the other hand, in each of the comparative examples and the prior examples, the characteristics of either of them were inferior.
比較例1由於第2貴金屬層之表面粗度Ra(B)過高,故而若於100gf之高滑動負載下,數滑動次數自50次成為100次,則接觸電阻增大,又,彎曲加工性較差。比較例2由於第1貴金屬層之硬度過低,故而若於100gf之高滑動負載下,數滑動次數自50次成為100次,則接觸電阻增大,又,耐摩耗性較差。先前例1由於第2貴金屬層之被覆厚度薄於第1貴金屬層之表面之算術平均粗糙度Ra=(A)μm,故而若於100gf之高滑動負載下,數滑動次數自50次成為100次,則接觸電阻增大。該等比較例與先前例均 未滿足實用等級。 In Comparative Example 1, since the surface roughness Ra (B) of the second noble metal layer is too high, if the number of sliding times is 100 times from 50 times under a sliding load of 100 gf, the contact resistance is increased and the bending workability is improved. Poor. In Comparative Example 2, since the hardness of the first noble metal layer was too low, if the number of sliding times was 100 times from 50 times under a sliding load of 100 gf, the contact resistance was increased and the abrasion resistance was inferior. In the first example, since the coating thickness of the second noble metal layer is thinner than the arithmetic mean roughness Ra of the surface of the first noble metal layer (=A) μm, the number of sliding times becomes 100 times from 50 times under a sliding load of 100 gf. , the contact resistance increases. These comparative examples and previous examples are The utility level is not met.
[產業上之可利用性] [Industrial availability]
本發明之電氣接點材料只要為通常之接觸式之電氣接點,則無論何種類型,均可適宜地使用。尤其因耐磨耗性與耐蝕性優異,故而可尤其適宜地用作例如:適於汽車車載之室內外滑動接點、或磁簧開關、馬達用換向器(commutator)接點及刷(brush)材料、攝影機座架接點用開關等電氣接點用之材料。 The electrical contact material of the present invention can be suitably used regardless of the type as long as it is a normal contact type electrical contact. In particular, since it is excellent in abrasion resistance and corrosion resistance, it can be suitably used, for example, as an indoor/outdoor sliding contact for a vehicle, or a reed switch, a commutator contact for a motor, and a brush (brush). Materials for electrical contacts such as materials and switches for camera mount contacts.
以上,將本發明與其實施態樣一併進行了說明,但認為只要本文中未特別指定,則對於說明本發明之所有細節亦不作限定,應於不違背隨附之申請專利範圍中所示之發明精神與範圍之情況下寬泛地進行解釋。 The invention has been described above in connection with the embodiments thereof, but it is to be understood that all the details of the invention are not to be construed as being limited to the scope of the accompanying claims. The invention is broadly explained in the context of the spirit and scope of the invention.
1‧‧‧導電性基體 1‧‧‧Electrically conductive substrate
2‧‧‧第1貴金屬層 2‧‧‧1st precious metal layer
3‧‧‧第2貴金屬層 3‧‧‧2nd precious metal layer

Claims (11)

  1. 一種電氣接點材料,其係於導電性基體之表面上具有第1貴金屬層,且於上述第1貴金屬層之表面上具有第2貴金屬層者,其特徵在於:上述第1貴金屬層之表面之算術平均粗糙度Ra=A μm為A<1,且該第1貴金屬層之硬度Hv為150以上,並且上述第2貴金屬層之厚度超過A μm且為1μm以下,且該第2貴金屬層之表面之算術平均粗糙度Ra=B μm為B≦0.1。 An electrical contact material having a first noble metal layer on a surface of a conductive substrate and having a second noble metal layer on a surface of the first noble metal layer, wherein a surface of the first noble metal layer is The arithmetic mean roughness Ra=A μm is A<1, and the hardness Hv of the first noble metal layer is 150 or more, and the thickness of the second noble metal layer exceeds A μm and is 1 μm or less, and the surface of the second noble metal layer The arithmetic mean roughness Ra = B μm is B ≦ 0.1.
  2. 如申請專利範圍第1項之電氣接點材料,其中上述A之值為0.001以上且未達0.500。 For example, in the electrical contact material of claim 1, wherein the value of A above is 0.001 or more and less than 0.500.
  3. 如申請專利範圍第1或2項之電氣接點材料,其中上述第1貴金屬層及第2貴金屬層分別由金、金合金、銀、銀合金、鉑、鉑合金、銦、銦合金、錫、錫合金、鈀、鈀合金、釕、釕合金、銠、銠合金、鋨、鋨合金、銥、銥合金中之任一種所構成。 The electrical contact material of claim 1 or 2, wherein the first precious metal layer and the second precious metal layer are respectively gold, gold alloy, silver, silver alloy, platinum, platinum alloy, indium, indium alloy, tin, It is composed of any one of tin alloy, palladium, palladium alloy, niobium, tantalum alloy, niobium, tantalum alloy, niobium, tantalum alloy, niobium and niobium alloy.
  4. 如申請專利範圍第1或2項中任一項之電氣接點材料,其中上述第1貴金屬層由鈀、鈀合金、釕、釕合金、銠、銠合金、鋨、鋨合金、銥、銥合金中之任一種所構成。 The electrical contact material according to any one of claims 1 to 2, wherein the first noble metal layer is made of palladium, palladium alloy, ruthenium, iridium alloy, ruthenium, osmium alloy, ruthenium, osmium alloy, ruthenium or iridium alloy. Any of them.
  5. 如申請專利範圍第1或2項中任一項之電氣接點材料,其中上述第2貴金屬層由金、金合金、銀、銀合金、鉑、鉑合金、銦、銦合金、錫、錫合金中之任一種所構成。 The electrical contact material according to any one of claims 1 to 2, wherein the second precious metal layer is made of gold, gold alloy, silver, silver alloy, platinum, platinum alloy, indium, indium alloy, tin, tin alloy. Any of them.
  6. 如申請專利範圍第1或2項中任一項之電氣接點材料,其中上述導電性基體與上述第1貴金屬層之間至少具有1層底層金屬層。 The electrical contact material according to any one of claims 1 to 2, wherein the conductive substrate and the first noble metal layer have at least one underlying metal layer.
  7. 如申請專利範圍第6項之電氣接點材料,其中上述底層金屬層由鎳、鎳合金、鈷、鈷合金中之任一種所構成。 The electrical contact material of claim 6, wherein the underlying metal layer is composed of any one of nickel, a nickel alloy, cobalt, and a cobalt alloy.
  8. 如申請專利範圍第6項之電氣接點材料,其中上述底層金屬層之厚度為0.05~3.00μm。 For example, the electrical contact material of claim 6 wherein the thickness of the underlying metal layer is 0.05 to 3.00 μm.
  9. 如申請專利範圍第1或2項中任一項之電氣接點材料,其中上述導電性基體由銅、銅合金、鐵、鐵合金、鋁、鋁合金中之任一種所構成。 The electrical contact material according to any one of claims 1 to 2, wherein the conductive substrate is made of any one of copper, a copper alloy, iron, an iron alloy, aluminum, and an aluminum alloy.
  10. 如申請專利範圍第1或2項中任一項之電氣接點材料,其中上述導電性基體之母相之平均結晶粒徑為5μm以下。 The electrical contact material according to any one of claims 1 to 2, wherein the mother phase of the conductive substrate has an average crystal grain size of 5 μm or less.
  11. 一種申請專利範圍第1至10項中任一項之電氣接點材料之製造方法,其特徵在於:利用電鍍法設置上述第1貴金屬層及第2貴金屬層之至少一層。 A method of producing an electrical contact material according to any one of claims 1 to 10, characterized in that at least one of the first noble metal layer and the second precious metal layer is provided by a plating method.
TW103103893A 2014-02-05 2014-02-05 Electrical contact material and manufacturing method thereof TWI557750B (en)

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EP3557596A4 (en) * 2016-12-19 2019-11-27 Tanaka Kikinzoku Kogyo K.K. Tape-like contact and method for manufacturing same

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TW201333987A (en) * 2011-11-24 2013-08-16 Nitto Denko Corp Transparent conductive film
TWI407469B (en) * 2006-03-17 2013-09-01 Furukawa Electric Co Ltd Material for electric contact and method of producing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI407469B (en) * 2006-03-17 2013-09-01 Furukawa Electric Co Ltd Material for electric contact and method of producing the same
TW201333987A (en) * 2011-11-24 2013-08-16 Nitto Denko Corp Transparent conductive film

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