TWI585244B - Sn-plated materials for electronic parts - Google Patents
Sn-plated materials for electronic parts Download PDFInfo
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- TWI585244B TWI585244B TW104142467A TW104142467A TWI585244B TW I585244 B TWI585244 B TW I585244B TW 104142467 A TW104142467 A TW 104142467A TW 104142467 A TW104142467 A TW 104142467A TW I585244 B TWI585244 B TW I585244B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
- C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0607—Wires
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/02—Contact members
- H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
Description
本發明關於一種適合用作電子零件，特別為連接器、端子等之導電性彈簧材料之鍍Sn材料。 The present invention relates to a Sn-plated material suitable for use as an electronic component, particularly a conductive spring material such as a connector or terminal.
作為端子、連接器等之導電性彈簧材料，使用經實施Sn鍍敷之銅或銅合金條(以下，稱為「鍍Sn材料」)。一般地，鍍Sn材料藉由以下步驟製造：在連續鍍敷作業線進行脫脂以及酸洗後，藉由電鍍法形成Cu基底鍍層，接著藉由電鍍法形成Sn層，最後實施回流焊處理，使Sn層熔融。 As the conductive spring material such as a terminal or a connector, a copper or copper alloy strip (hereinafter referred to as "Sn-plated material") subjected to Sn plating is used. Generally, the Sn-plated material is produced by performing a degreasing and pickling on a continuous plating line, forming a Cu-based plating layer by electroplating, then forming a Sn layer by electroplating, and finally performing a reflow process. The Sn layer is melted.
在對上述鍍Sn材料進行壓製加工來製造連接器等時，利用壓板來按壓鍍Sn材料，但由於壓板與鍍Sn材料表面接觸，產生了自鍍Sn材料之Sn鍍層產生Sn粉並混入壓製機之問題。 When the above-mentioned Sn-plated material is subjected to press working to manufacture a connector or the like, the Sn plate material is pressed by the press plate, but since the press plate is in contact with the surface of the Sn-plated material, Sn powder is generated from the Sn plating layer of the Sn-plated material and mixed into the press. The problem.
此外，一般地，在連接器等之組裝作業線，設置有用於檢測表面缺陷之檢測器，藉由向端子表面照射光並對其反射光進行檢測來檢測出缺陷。因此，為了高精度地檢測缺陷，要求端子之表面光澤較高，即要求導電性彈簧材料之表面光澤較高。 Further, generally, a detector for detecting a surface defect is provided on an assembly line such as a connector, and a defect is detected by irradiating light to the surface of the terminal and detecting the reflected light. Therefore, in order to detect defects with high precision, it is required that the surface gloss of the terminal is high, that is, the surface gloss of the conductive spring material is required to be high.
隨著近年來之連接器之小型化，對於鍍Sn材料，強烈要求抑制上述Sn 粉之產生以及良好之表面光澤。 With the miniaturization of connectors in recent years, it is strongly required to suppress the above Sn for the Sn-plated material. Powder production and good surface gloss.
對於上述Sn粉之問題，在專利文獻1中公開有以下方法：在對銅合金條進行基底鍍敷、Sn鍍敷後，控制回流焊處理之風扇之頻率，藉此使Cu-Sn合金層露出至鍍Sn材料之最表面，使該露出之Cu-Sn合金層面積率為0.5~4%，使每0.033mm2之個數為100~900個。 In the above-mentioned problem of Sn powder, Patent Document 1 discloses a method of controlling the frequency of a fan of a reflow process after performing base plating and Sn plating on a copper alloy strip, thereby exposing the Cu-Sn alloy layer. To the outermost surface of the Sn-plated material, the exposed Cu-Sn alloy layer has an area ratio of 0.5 to 4%, and the number per 0.033 mm 2 is 100 to 900.
在專利文獻2中公開有以下方法：在銅合金條進行基底鍍敷、Sn鍍敷後，在藉由回流焊爐進行加熱、空冷後，藉由水冷，使回流焊後之Sn層中以50~1000個/μm2之個數密度存在粒徑為10~100nm之Cu-Sn合金粒子。 Patent Document 2 discloses a method in which a copper alloy strip is subjected to base plating and Sn plating, and after being heated by a reflow furnace and air-cooled, water cooling is performed to make the Sn layer after reflow soldering 50. A number of ~1000 particles/μm 2 has Cu-Sn alloy particles having a particle diameter of 10 to 100 nm.
現有技術文獻 Prior art literature
專利文獻 Patent literature
專利文獻1：日本專利第5389097號公報 Patent Document 1: Japanese Patent No. 5389097
專利文獻2：日本專利第5587935號公報 Patent Document 2: Japanese Patent No. 5587935
上述鍍Sn材料於抑制Sn粉之產生而言有效，但卻不足以滿足伴隨近年來之連接器之小型化之抑制Sn粉產生之要求。並且，為了高精度地進行表面檢查，要求提高表面光澤。 The Sn-plated material described above is effective for suppressing the generation of Sn powder, but is insufficient to satisfy the demand for suppressing the generation of Sn powder accompanying the miniaturization of connectors in recent years. Further, in order to perform surface inspection with high precision, it is required to improve surface gloss.
本發明之目的在於進一步改良以抑制Sn粉產生，同時得到良好之表面光澤。據本發明之發明人所知，以往並未發現抑制Sn粉產生並 且可得到良好之表面光澤之發明。 The object of the present invention is to further improve the suppression of the generation of Sn powder while obtaining a good surface gloss. According to the inventors of the present invention, it has not been found in the past to suppress the generation of Sn powder and And the invention of good surface gloss can be obtained.
本發明係鑒於上述課題完成者，其目的在於提供一種作為連接器、端子等導電性彈簧材料，防止Sn粉之產生並具有良好之表面光澤之鍍Sn材料。 The present invention has been made in view of the above problems, and an object of the invention is to provide a Sn-plated material which is a conductive spring material such as a connector or a terminal and which prevents the generation of Sn powder and has a good surface gloss.
本發明人潛心研究之結果，發現為了抑制Sn粉之產生，有效的是提高鍍Sn材料之表面平滑性。在壓製加工時，藉由壓板保持鍍Sn材料時Sn層受到刮擦，而產生Sn粉。壓板以一定之負載按壓鍍Sn材料，但若鍍Sn材料之表面粗糙度較大，則如圖1所示，由於與壓板接觸之面積變小，壓板與鍍Sn材料之接觸部之每單位面積上之負載變大，壓板相對於鍍Sn材料之嵌入量變大。其結果為，鍍Sn材料被刮擦之量變多，Sn粉之產生量亦變多。 As a result of intensive research, the inventors have found that in order to suppress the generation of Sn powder, it is effective to improve the surface smoothness of the Sn-plated material. At the time of press working, the Sn layer is scratched while the Sn material is being plated by the press plate to generate Sn powder. The platen presses the Sn-plated material with a certain load, but if the surface roughness of the Sn-plated material is large, as shown in FIG. 1, since the area in contact with the platen becomes small, the unit area of the contact portion between the platen and the Sn-plated material is per unit area. The load on the upper side becomes larger, and the amount of insertion of the press plate with respect to the Sn-plated material becomes large. As a result, the amount of scratched Sn material is increased, and the amount of Sn powder is also increased.
反之，若鍍Sn材料之表面粗糙度較小，則如圖2所示，由於與壓板接觸之面積變大，壓板與鍍Sn材料之接觸部之每單位面積上之負載變小，壓板相對於鍍Sn材料之嵌入量變小。其結果為，鍍Sn材料被刮擦之量變少，Sn粉之產生量亦變少。而且，若鍍Sn材料之表面粗糙度變小，則表面光澤提高。 On the other hand, if the surface roughness of the Sn-plated material is small, as shown in FIG. 2, since the area in contact with the platen becomes larger, the load per unit area of the contact portion between the platen and the Sn-plated material becomes smaller, and the platen is opposed to The amount of embedded Sn-plated material becomes small. As a result, the amount of scratched Sn material is reduced, and the amount of Sn powder is also reduced. Further, if the surface roughness of the Sn-plated material is small, the surface gloss is improved.
為了減小鍍Sn材料之表面粗糙度，需要進行以下方法：藉由回流焊處理，對經實施Sn鍍敷之銅合金條進行加熱後，噴霧出冷卻水至鍍Sn材料之表面(以下，稱為「霧狀水冷」)，接著投入鍍Sn材料。 In order to reduce the surface roughness of the Sn-plated material, the following method is required: after the Sn-plated copper alloy strip is heated by reflow processing, the cooling water is sprayed to the surface of the Sn-plated material (hereinafter, It is "fogging water cooling"), followed by the plating of Sn material.
一般而言，藉由回流焊處理加熱後之鍍敷材料之冷卻方法為在加熱後投入水槽，或者數秒空冷後，投入水槽之方法。該情況下，由於 藉由回流焊加熱而熔融之Sn在投入水槽後立即凝固，因此如圖3所示，此Sn之凝固組織之形態成為柱狀。因此，其剖面形狀如圖1，表面粗糙度變大。 In general, the cooling method of the plating material after heating by reflow processing is a method of putting it into a water tank after heating, or air cooling for several seconds, and then putting it into a water tank. In this case, due to Since Sn which is melted by reflow heating is solidified immediately after being placed in the water tank, the form of the solidified structure of Sn becomes a columnar shape as shown in Fig. 3 . Therefore, the cross-sectional shape thereof is as shown in Fig. 1, and the surface roughness becomes large.
另一方面，若在將藉由回流焊處理加熱後之鍍敷材料投入水槽之前進行霧狀水冷，則由於噴霧出之水粒子附著於表面而冷卻，因此如圖4所示，此Sn之凝固組織之形態成為放射狀。因此其剖面形狀如圖2，表面粗糙度變小。 On the other hand, when the plating material heated by the reflow process is placed in the water tank before being sprayed into the water tank, the sprayed water particles adhere to the surface and are cooled, so that the solidification of the Sn is as shown in FIG. The shape of the tissue is radial. Therefore, the cross-sectional shape is as shown in Fig. 2, and the surface roughness becomes small.
如此，對藉由回流焊處理加熱後之鍍敷材料進行霧狀水冷後，進行投入水槽之冷卻，使Sn之凝固組織形態呈放射狀，減小表面粗糙度，藉此可抑制Sn粉之產生，並可得到良好之表面光澤。 In this manner, the plated material heated by the reflow process is subjected to a mist-like water cooling, and then cooled in a water tank to radially form the solidified structure of Sn, thereby reducing the surface roughness, thereby suppressing the generation of Sn powder. And can get a good surface gloss.
即，本發明包括： That is, the present invention includes:
(1)一種鍍Sn材料，其在銅或銅合金條之基材上具有經實施回流焊處理之Sn鍍層，其特徵在於：回流焊Sn鍍層由上側之Sn層與下側之Cu-Sn合金層構成，在鍍Sn材料之最表面，每35mm2存在1個以上放射狀之Sn凝固組織，鍍Sn材料之最表面之壓延直角方向之表面粗糙度Ra為0.05μm以下。 (1) A Sn-plated material having a Sn-plated layer subjected to reflow processing on a substrate of a copper or copper alloy strip, characterized in that the Sn-plated layer is reflowed from the Sn layer on the upper side and the Cu-Sn alloy on the lower side. In the layer structure, one or more radial Sn solidified structures are present every 35 mm 2 on the outermost surface of the Sn-plated material, and the surface roughness Ra of the outermost surface of the Sn-plated material in the right-angle direction is 0.05 μm or less.
(2)如(1)之鍍Sn材料，其特徵在於，露出至最表面之Cu-Sn合金層之面積率為40%以下，自表面觀察時之上述露出之Cu-Sn合金層之結晶粒徑為3μm以下。 (2) The Sn-plated material according to (1), characterized in that the area ratio of the Cu-Sn alloy layer exposed to the outermost surface is 40% or less, and the crystal grains of the exposed Cu-Sn alloy layer are observed from the surface. The diameter is 3 μm or less.
(3)如(1)或(2)之鍍Sn材料，其中，銅或銅合金條之基材上藉由Cu基底鍍層、或Ni基底鍍層、或將Ni以及Cu按照該順序積層而成之Ni/Cu雙層基底鍍層被覆，並在其上具有回流焊Sn鍍層。 (3) The Sn-plated material according to (1) or (2), wherein the substrate of the copper or copper alloy strip is formed by a Cu-based plating layer or a Ni-based plating layer, or Ni and Cu are laminated in this order. The Ni/Cu bilayer base coating is coated with a reflowed Sn plating thereon.
(4)一種鍍Sn材料之製造方法，其在銅或銅合金條之基材上，在形成Sn鍍層或按順序形成Cu、Sn鍍層後，藉由回流焊處理，在基材上介隔Cu-Sn合金層而形成Sn層，其特徵在於：使上述Cu鍍層之厚度為0~0.5μm、上述Sn鍍層之厚度為0.5~1.5μm，在上述回流焊處理中，以溫度300~600℃加熱1~30秒後，噴霧出20~90℃之冷卻水，接著投入至20~90℃之水槽。 (4) A method for producing a Sn-plated material, which is formed on a substrate of a copper or copper alloy strip by forming a Sn plating layer or sequentially forming a Cu, Sn plating layer, and then reflowing the substrate to form a Cu on the substrate. a Sn alloy layer to form a Sn layer, wherein the Cu plating layer has a thickness of 0 to 0.5 μm, and the Sn plating layer has a thickness of 0.5 to 1.5 μm, and is heated at a temperature of 300 to 600 ° C in the reflow process. After 1 to 30 seconds, spray 20~90 °C of cooling water, and then put it into the 20~90 °C water tank.
(5)一種鍍Sn材料之製造方法，其在銅或銅合金條之基材上按順序形成Ni、Cu、Sn鍍層後，藉由回流焊處理，在基材上被覆Ni基底鍍層或Ni/Cu雙層基底鍍層，並介隔Cu-Sn合金層而形成Sn層，其特徵在於：使上述Ni鍍層為0.05~3μm、上述Cu鍍層之厚度為0.05~0.5μm、上述Sn鍍層之厚度為0.5~1.5μm，在上述回流焊處理中，以溫度300~600℃加熱1~30秒後，噴霧出20~90℃之冷卻水，接著投入至20~90℃之水槽。 (5) A method for producing a Sn-plated material, which is formed by sequentially forming Ni, Cu, and Sn plating on a substrate of a copper or copper alloy strip, and then coating a Ni-based plating layer or Ni/ on the substrate by reflow processing. a Cu double-layer base plating layer and a Cu-Sn alloy layer interposed to form an Sn layer, wherein the Ni plating layer is 0.05 to 3 μm, the Cu plating layer has a thickness of 0.05 to 0.5 μm, and the Sn plating layer has a thickness of 0.5. ~1.5 μm, in the above reflow process, after heating at 300 to 600 ° C for 1 to 30 seconds, the cooling water of 20 to 90 ° C is sprayed, and then poured into a water tank of 20 to 90 ° C.
(6)一種電子零件，其具備(1)~(3)中任一項之鍍Sn材料。 (6) An electronic component comprising the Sn-plated material according to any one of (1) to (3).
藉由本發明之鍍Sn材料，特別是對於用於汽車以及電子零件等之端子，可使接合時之***力低，並高精度地實施端子組裝時之表面檢查。 According to the Sn-plated material of the present invention, particularly for terminals for automobiles and electronic parts, the insertion force at the time of joining can be made low, and the surface inspection at the time of terminal assembly can be performed with high precision.
圖1為鍍Sn材料之最表面之表面粗糙度較大之情況下之剖面示意圖。 Fig. 1 is a schematic cross-sectional view showing a case where the surface roughness of the outermost surface of the Sn-plated material is large.
圖2為鍍Sn材料之最表面之表面粗糙度較小之情況下之剖面示意圖。 Fig. 2 is a schematic cross-sectional view showing a case where the surface roughness of the outermost surface of the Sn-plated material is small.
圖3為在藉由回流焊處理而加熱後投入水槽之情況下之鍍Sn材料的蝕刻後之最表面組織照片。 Fig. 3 is a photograph showing the most surface texture after etching of the Sn-plated material in the case where it is heated by a reflow process and then placed in a water tank.
圖4為在藉由回流焊處理加熱後實施霧狀水冷，接著投入水槽之情況下之鍍Sn材料的蝕刻後之最表面組織照片。 Fig. 4 is a photograph showing the most surface texture after etching of the Sn-plated material in the case where the mist-like water cooling is performed by heating after the reflow process and then placed in a water tank.
圖5為鏡面反射率測定方法之說明圖。 Fig. 5 is an explanatory view showing a method of measuring specular reflectance.
以下，對於本發明之鍍Sn材料之一實施形態進行說明。再者，本發明中，除非另有說明，則所謂%表示質量%。 Hereinafter, an embodiment of the Sn-plated material of the present invention will be described. Further, in the present invention, the meaning "%" means mass% unless otherwise stated.
(1)基材之組成 (1) Composition of the substrate
作為構成鍍Sn材料之基材之銅條，可使用純度99.9%以上之精銅、無氧銅，此外，作為銅合金條，可根據所要求之強度、導電性，使用公知之銅合金。作為公知之銅合金，例如可以舉出Cu-Sn-P系合金、Cu-Zn系合金、Cu-Ti系合金、Cu-Ni-Si系合金、Cu-Sn-Zn系合金、Cu-Zr系合金等。 As the copper strip constituting the substrate on which the Sn-plated material is formed, fine copper having a purity of 99.9% or more and oxygen-free copper can be used. Further, as the copper alloy strip, a known copper alloy can be used depending on the required strength and conductivity. Examples of the known copper alloy include a Cu-Sn-P alloy, a Cu-Zn alloy, a Cu-Ti alloy, a Cu-Ni-Si alloy, a Cu-Sn-Zn alloy, and a Cu-Zr system. Alloys, etc.
(2)放射狀之Sn凝固組織 (2) Radial Sn solidification structure
藉由如前所述地進行霧狀水冷，熔融之Sn凝固為放射狀。若每35mm2存在1個以上該放射狀之Sn凝固組織，則表面粗糙度Ra成為0.05μm以下。放射狀之Sn凝固組織之個數在本發明之效果得到發揮之範圍內並無特別限制，但在製造上難以超過10個。 The molten Sn is solidified into a radial shape by performing mist-like water cooling as described above. When one or more of the radial Sn solidified structures are present per 35 mm 2 , the surface roughness Ra is 0.05 μm or less. The number of the radial Sn solidified structures is not particularly limited insofar as the effects of the present invention are exhibited, but it is difficult to manufacture more than 10 in terms of production.
(3)表面粗糙度 (3) Surface roughness
在回流焊處理後之鍍Sn材料之最表面，壓延直角方向之表面粗糙度Ra為0.05μm以下。較佳為Ra為0.03μm以下，更佳為Ra為0.02μm以下。 若該壓延直角方向之表面粗糙度Ra過大，則無法抑制Sn粉之產生，亦無法得到良好之表面光澤。表面粗糙度之下限在本發明之效果得到發揮之範圍內並無特別限制，但在製造上Ra難以小於0.001μm。 On the outermost surface of the Sn-plated material after the reflow process, the surface roughness Ra in the direction perpendicular to the rolling is 0.05 μm or less. Preferably, Ra is 0.03 μm or less, and more preferably Ra is 0.02 μm or less. If the surface roughness Ra in the direction perpendicular to the rolling is too large, the generation of the Sn powder cannot be suppressed, and a good surface gloss cannot be obtained. The lower limit of the surface roughness is not particularly limited insofar as the effect of the present invention is exerted, but Ra is hardly less than 0.001 μm in the production.
(4)Cu-Sn系合金層 (4) Cu-Sn alloy layer
若在上述Sn鍍敷後實施回流焊處理，則基材及/或Cu基底鍍層之Cu擴散至Sn鍍層，在Sn鍍層之下側形成有Cu-Sn合金層。通常具有Cu6Sn5及/或Cu3Sn之組成，但亦可含有上述基底鍍敷之成分或以銅合金為基材時之添加元素。 When the reflow process is performed after the Sn plating, the Cu of the substrate and/or the Cu-based plating layer is diffused to the Sn plating layer, and the Cu-Sn alloy layer is formed under the Sn plating layer. Usually, it has a composition of Cu 6 Sn 5 and/or Cu 3 Sn, but may also contain a component of the above-mentioned base plating or an additive element when a copper alloy is used as a substrate.
與Sn層相比，Cu-Sn合金層為硬質，因此，可藉由使其露出至鍍Sn材料之最表面而進一步抑制Sn粉之產生。但露出至鍍Sn材料之最表面之Cu-Sn合金層之面積率為40%以下。較佳為35%以下，更佳為30%以下。若面積率過大，則Sn鍍層之表面粗糙度Ra變得過大，無法得到良好之表面光澤。 The Cu-Sn alloy layer is harder than the Sn layer, and therefore, the Sn powder can be further suppressed by being exposed to the outermost surface of the Sn-plated material. However, the area ratio of the Cu-Sn alloy layer exposed to the outermost surface of the Sn-plated material is 40% or less. It is preferably 35% or less, more preferably 30% or less. When the area ratio is too large, the surface roughness Ra of the Sn plating layer becomes too large, and a good surface gloss cannot be obtained.
而且，露出至最表面之Cu-Sn合金層之結晶粒徑為3μm以下。較佳為2.5μm以下，更佳為2μm以下。若結晶粒徑過大，則Sn鍍層之壓延直角方向之表面粗糙度Ra變得過大，無法得到良好之表面光澤。結晶粒徑之下限在本發明之效果得到發揮之範圍內並無特別限制，但製造上難以小於0.1μm。 Further, the Cu-Sn alloy layer exposed to the outermost surface has a crystal grain size of 3 μm or less. It is preferably 2.5 μm or less, more preferably 2 μm or less. When the crystal grain size is too large, the surface roughness Ra of the Sn plating layer in the direction perpendicular to the rolling direction becomes too large, and a good surface gloss cannot be obtained. The lower limit of the crystal grain size is not particularly limited insofar as the effects of the present invention are exhibited, but it is difficult to manufacture by less than 0.1 μm.
(5)製造方法 (5) Manufacturing method
本發明之實施方式之鍍Sn材料可藉由以下步驟製造：在連續鍍敷作業線中，在對作為基材之銅或銅合金條之表面進行脫脂以及酸洗後，藉由電鍍法形成基底鍍層，接著藉由公知之電鍍法形成Sn層，最後實施回流焊處 理，使Sn層熔融。亦可省略基底鍍層。 The Sn-plated material of the embodiment of the present invention can be produced by forming a substrate by electroplating after degreasing and pickling the surface of the copper or copper alloy strip as a substrate in a continuous plating line. Plating, then forming a Sn layer by well-known electroplating, and finally implementing reflow soldering The Sn layer is melted. The base plating may also be omitted.
雖然可不進行Cu基底鍍敷，但在進行Cu基底鍍敷之情況下，其厚度設為0.5μm以下。較佳為0.4μm以下，更佳為0.35μm以下。若厚度過大，則露出之Cu-Sn合金層之結晶粒徑變得過大，Sn鍍層之壓延直角方向之表面粗糙度Ra變得過大，無法得到良好之表面光澤。 Although Cu substrate plating may not be performed, when Cu substrate plating is performed, the thickness is set to 0.5 μm or less. It is preferably 0.4 μm or less, more preferably 0.35 μm or less. When the thickness is too large, the crystal grain size of the exposed Cu-Sn alloy layer becomes too large, and the surface roughness Ra of the Sn plating layer in the direction perpendicular to the rolling direction becomes too large, and a good surface gloss cannot be obtained.
為了提高耐熱性，亦可在Cu基底鍍敷之前進行Ni基底鍍敷。該情況下，Ni基底鍍敷之厚度並無特別限制，但若厚度低於0.05μm則Ni基底鍍敷之效果無法得到發揮，若超過3μm，則不僅經濟性差，亦導致彎曲加工性劣化。因此Ni基底鍍敷之厚度較佳為0.05~3μm。此外，Ni基底鍍敷後之Cu基底鍍敷之厚度並無特別限制，但若厚度低於0.05μm或超過0.5μm，則Ni基底鍍敷後之Cu基底鍍敷之效果無法發揮。因此Ni基底鍍敷後之Cu基底鍍敷之厚度較佳為0.05~0.5μm。 In order to improve heat resistance, Ni substrate plating may be performed before Cu substrate plating. In this case, the thickness of the Ni-based plating is not particularly limited. However, when the thickness is less than 0.05 μm, the effect of Ni-based plating cannot be exhibited. When the thickness exceeds 3 μm, the economical performance is deteriorated and the bending workability is deteriorated. Therefore, the thickness of the Ni substrate plating is preferably 0.05 to 3 μm. Further, the thickness of the Cu-based plating after the Ni-based plating is not particularly limited, but if the thickness is less than 0.05 μm or more than 0.5 μm, the effect of Cu-based plating after Ni-based plating cannot be exhibited. Therefore, the thickness of the Cu substrate plating after the Ni substrate plating is preferably 0.05 to 0.5 μm.
Sn鍍敷之厚度為0.5~1.5μm。較佳為0.6~1.2μm，更佳為0.7~1.1μm，若Sn鍍敷之厚度過小，則回流焊處理後之Sn層之厚度變得過小，結果Sn鍍層之壓延直角方向之表面粗糙度Ra變得過大，以及Cu-Sn合金層之面積率變得過大，無法得到良好之表面光澤。Sn鍍敷厚度之上限在本發明之效果得到發揮之範圍內並無特別限制，但由於當Sn鍍敷厚度較厚時經濟性變差，因此上限設為1.5μm。 The thickness of Sn plating is 0.5 to 1.5 μm. It is preferably 0.6 to 1.2 μm, more preferably 0.7 to 1.1 μm. If the thickness of the Sn plating is too small, the thickness of the Sn layer after the reflow process becomes too small, and as a result, the surface roughness Ra of the Sn plating in the right angle direction is obtained. It becomes too large, and the area ratio of the Cu-Sn alloy layer becomes too large, and a good surface gloss cannot be obtained. The upper limit of the thickness of the Sn plating is not particularly limited as long as the effect of the present invention is exerted. However, since the economy is deteriorated when the thickness of the Sn plating is thick, the upper limit is made 1.5 μm.
回流焊處理藉由以下之方法進行：將鍍Sn材料以爐內溫度300~600℃加熱1~30秒後，噴霧出20~90℃之冷卻水至鍍Sn材料之表面，接著將鍍Sn材料投入至20~90℃之水槽。 The reflow process is carried out by heating the plated Sn material at a furnace temperature of 300 to 600 ° C for 1 to 30 seconds, and then spraying 20 to 90 ° C of cooling water to the surface of the Sn-plated material, followed by plating the Sn material. Put into the sink at 20~90 °C.
若加熱溫度小於300℃及/或加熱時間小於1秒時，則存在 Sn之熔融不充分之可能性，製造不穩定。反之，若加熱溫度超過600℃及/或加熱時間超過30秒，則露出至最表面之Cu-Sn合金層之面積率超過40%，其結晶粒徑超過3μm，壓延直角方向之表面粗糙度Ra超過0.05μm，無法得到良好之表面光澤。 If the heating temperature is less than 300 ° C and / or the heating time is less than 1 second, then there is The possibility that the melting of Sn is insufficient is unstable. On the other hand, if the heating temperature exceeds 600 ° C and/or the heating time exceeds 30 seconds, the area ratio of the Cu-Sn alloy layer exposed to the outermost surface exceeds 40%, the crystal grain size exceeds 3 μm, and the surface roughness Ra in the right angle direction is rolled. Above 0.05 μm, a good surface gloss cannot be obtained.
如前所述，藉由在加熱後噴霧出冷卻水，可得到放射狀之Sn凝固組織。而且，噴霧出之水粒子附著於加熱後之鍍敷材料之表面，而此部分驟冷，抑制Cu-Sn合金層之成長。另一方面，水粒子未附著之部分並未驟冷，Cu-Sn合金層之成長未受抑制。因此，可在加熱後之鍍敷表面產生局部之冷卻速度差，亦具有使露出至鍍敷材料之表面之Cu-Sn合金層之結晶粒徑細微化之效果。 As described above, a radial Sn solidified structure can be obtained by spraying cooling water after heating. Further, the sprayed water particles adhere to the surface of the heated plating material, and this portion is quenched to suppress the growth of the Cu-Sn alloy layer. On the other hand, the portion where the water particles did not adhere was not quenched, and the growth of the Cu-Sn alloy layer was not suppressed. Therefore, a local cooling rate difference can be generated on the plated surface after heating, and the crystal grain size of the Cu-Sn alloy layer exposed to the surface of the plating material can be made fine.
實施例 Example
以下表示實施例，但意圖並不在於藉由以下之實施例來限定本發明。 The examples are shown below, but are not intended to limit the invention by the following examples.
以精銅為原料，鑄造出以成為表1所示之比例(質量%)之方式添加有各元素之鑄錠，在900℃以上進行熱壓延至厚度10mm，並在面削表面之氧化皮後，重複進行冷壓延與熱處理，最終製成厚度0.2mm之板(基材)。 An ingot in which each element is added in a ratio (% by mass) shown in Table 1 is cast as a raw material, and is hot-rolled to a thickness of 10 mm at 900 ° C or higher, and after the surface is peeled off. The cold rolling and heat treatment were repeated, and finally a plate (substrate) having a thickness of 0.2 mm was formed.
接著，對該基材之表面進行脫脂及酸洗後，藉由電鍍法按照Ni鍍層、Cu鍍層之順序形成基底鍍層，視情況省略Ni基底鍍敷以及Cu基底鍍敷，接著藉由電鍍法形成Sn鍍層。在實施Ni基底鍍敷之情況下，藉由硫酸浴(液溫約50℃，電流密度5A/dm2)進行電鍍，使Ni基底鍍敷之厚度為0.3μm。在實施Cu基底鍍敷之情況下，藉由硫酸浴(液溫約25℃，電流密度30A/dm2)進行電鍍。Sn鍍敷為藉由苯酚磺酸浴(液溫約35℃，電流密度12A/dm2)進行電鍍。Cu基底鍍層以及Sn鍍層之各鍍層厚度藉由調整電沉積時間來進行調整。 Next, after degreasing and pickling the surface of the substrate, a base plating layer is formed in the order of Ni plating layer or Cu plating layer by a plating method, and Ni base plating and Cu base plating are omitted as occasion demands, and then formed by electroplating. Sn plating. In the case of performing Ni-base plating, plating was performed by a sulfuric acid bath (liquid temperature: about 50 ° C, current density: 5 A/dm 2 ), and the thickness of the Ni-base plating was 0.3 μm. In the case of performing Cu substrate plating, electroplating was carried out by a sulfuric acid bath (liquid temperature of about 25 ° C, current density of 30 A/dm 2 ). Sn plating was performed by a phenolsulfonic acid bath (liquid temperature of about 35 ° C, current density of 12 A/dm 2 ). The thickness of each of the Cu base plating layer and the Sn plating layer is adjusted by adjusting the electrodeposition time.
接著，在加熱至300~650℃之爐中加熱1~30秒後，將70℃之冷卻水以霧狀進行噴灑後，投入到70℃之水槽。對於一部分實施例，加熱後，不進行霧狀之水冷便投入到70℃之水槽。 Next, after heating for 1 to 30 seconds in an oven heated to 300 to 650 ° C, the cooling water of 70 ° C was sprayed in a mist form, and then poured into a water tank of 70 ° C. For some of the examples, after heating, the water was cooled in a mist form and placed in a water tank of 70 °C.
對如此得到之各鍍Sn材料進行各項特性之評價。 Each of the Sn-plated materials thus obtained was evaluated for various characteristics.
(1)Sn鍍敷厚度 (1) Sn plating thickness
使用CT-1型電解式膜厚計(電測股份有限公司製造)，測定Sn鍍層之厚度。 The thickness of the Sn plating layer was measured using a CT-1 type electrolytic film thickness meter (manufactured by Electric Co., Ltd.).
(2)最表面之Sn凝固組織 (2) The most surface Sn solidification structure
將鍍Sn材料浸漬於65%苯酚磺酸水溶液5分鐘，使Sn凝固組織出現後，使用顯微鏡(Keyence公司(股)製造之VW-6000)觀察35mm2之範圍，如圖4般，測定Sn凝固組織之個數。 The Sn-plated material was immersed in a 65% phenolsulfonic acid aqueous solution for 5 minutes to expose the solidified structure of Sn, and a range of 35 mm 2 was observed using a microscope (VW-6000 manufactured by Keyence Co., Ltd.), and as shown in Fig. 4, Sn solidification was measured. The number of organizations.
(3)表面粗糙度 (3) Surface roughness
使用共焦顯微鏡(Lasertec(股)公司製造之HD100)，按照JIS B 0601標準測定鍍Sn材料之壓延直角方向之表面粗糙度Ra以及RSm。 The surface roughness Ra and RSm in the direction perpendicular to the rolling direction of the Sn-plated material were measured in accordance with JIS B 0601 using a confocal microscope (HD100 manufactured by Lasertec Co., Ltd.).
(4)露出至表面之Cu-Sn合金層之面積率 (4) Area ratio of Cu-Sn alloy layer exposed to the surface
使用FE-SEM(日本FEI(股)製造之XL30SFEG)，以750倍之倍率觀察0.017mm2之視野之反射電子像。由於露出至表面之Cu-Sn合金層與Sn層相比，呈較暗之圖像，因此將該圖像二值化，藉由求出Cu-Sn合金層之面積來算出面積率。二值化(binarization)係在高度範圍(height range)255中設定成170而進行。 A reflected electron image of a field of view of 0.017 mm 2 was observed at a magnification of 750 times using an FE-SEM (XL30SFEG manufactured by FEI Co., Ltd.). Since the Cu-Sn alloy layer exposed to the surface has a darker image than the Sn layer, the image is binarized, and the area ratio is calculated by determining the area of the Cu-Sn alloy layer. Binarization is performed by setting it to 170 in the height range 255.
(5)露出至最表面之Cu-Sn合金層之結晶粒徑 (5) Crystal grain size of the Cu-Sn alloy layer exposed to the outermost surface
使用FE-SEM(日本FEI(株)製造之XL30SFEG)，以2000倍之倍率觀察露出之Cu-Sn合金層之反射電子像。此後，隨機選擇10個Cu-Sn合金層，分別求出包含各Cu-Sn合金層之最大圓之直徑，將10個最大圓之直徑平均值作為Cu-Sn合金層之結晶粒徑。 The reflected electron image of the exposed Cu-Sn alloy layer was observed at a magnification of 2000 times using FE-SEM (XL30SFEG, manufactured by FEI Corporation, Japan). Thereafter, ten Cu-Sn alloy layers were randomly selected, and the diameter of the largest circle including each Cu-Sn alloy layer was determined, and the average diameter of the ten largest circles was defined as the crystal grain size of the Cu-Sn alloy layer.
(6)表面光澤 (6) Surface gloss
使用數位式變角度光澤度儀(日本電測工業(股)製造之VG-1D)，測定鍍Sn材料之鏡面反射率。如圖5所示，自投光部以30°之入射角射入光，利用受光部檢測以30°之角度在鍍Sn材料反射之光，藉此測定鍍Sn材料之鏡面反射率。由於自投光部直接受光時之鏡面反射率為100%，故該值越高，鍍Sn材料之表面光澤越良好。 The specular reflectance of the Sn-plated material was measured using a digital variable angle gloss meter (VG-1D manufactured by Nippon Denshoku Industries Co., Ltd.). As shown in FIG. 5, light was incident from the light projecting portion at an incident angle of 30°, and light reflected from the Sn-plated material was detected by the light-receiving portion at an angle of 30°, thereby measuring the specular reflectance of the Sn-plated material. Since the specular reflectance when the light is directly received from the light projecting portion is 100%, the higher the value, the better the surface gloss of the Sn-plated material.
(7)Sn粉 (7) Sn powder
將試料置於摩擦試驗裝置(斯加試驗機股份有限公司製造，斯加磨耗試驗機)上，將毛氈放在試料表面，在毛氈上負載30g之重量之狀態下，使毛氈以1cm之振幅在試料表面來回運動(掃描距離10mm，掃描速度13mm/s，來回次數30次)。 The sample was placed on a friction test device (manufactured by Ska Test Machine Co., Ltd., Saga Abrasion Tester), and the felt was placed on the surface of the sample, and the felt was loaded with a weight of 30 g on the felt to make the felt at an amplitude of 1 cm. The surface of the sample was moved back and forth (scanning distance 10 mm, scanning speed 13 mm/s, round trip times 30 times).
此後，觀察試料側之毛氈表面，目測評價Sn粉之附著程度。評價標準如下。若評價為△，則幾乎不產生Sn粉，在實際使用上無問題，若為○，則更佳。 Thereafter, the surface of the felt on the sample side was observed, and the degree of adhesion of the Sn powder was visually evaluated. The evaluation criteria are as follows. When the evaluation is Δ, Sn powder is hardly produced, and there is no problem in practical use, and if it is ○, it is more preferable.
○：未見Sn粉附著於毛氈。 ○: No Sn powder adhered to the felt.
△：可見Sn粉稀疏地附著於毛氈。 △: It can be seen that the Sn powder is sparsely attached to the felt.
×：可見Sn粉濃密地附著於毛氈。 ×: The Sn powder was densely attached to the felt.
將實施例示於表2及表3。 The examples are shown in Tables 2 and 3.
發明例1~39中，鍍Sn材料之最表面之壓延直角方向之表面粗糙度Ra均為0.05μm以下，每35mm2具有1個以上放射狀之Sn凝固組織，露出至最表面之Cu-Sn合金層之面積率為40%以下，Cu-Sn合金層露出至最表面之情況下，其結晶粒徑為3μm以下。該等鍍Sn材料之鏡面反射率為70%以上，可得到良好之表面光澤，抑制了Sn粉之產生。 In Inventive Examples 1 to 39, the surface roughness Ra of the outermost surface of the Sn-plated material is 0.05 μm or less in the right-angle direction, and has one or more radial Sn solidified structures per 35 mm 2 to expose the Cu-Sn to the outermost surface. The area ratio of the alloy layer is 40% or less, and when the Cu-Sn alloy layer is exposed to the outermost surface, the crystal grain size is 3 μm or less. The specular reflectance of the Sn-plated material is 70% or more, and a good surface gloss can be obtained, and the generation of Sn powder is suppressed.
比較例1係鍍敷時之Sn鍍敷厚度小於0.5μm之例。回流焊後之Sn層厚度未達0.2μm，露出至最表面之Cu-Sn合金層之面積率超過40%，壓延直角方向之Ra超過0.05μm，鏡面反射率未達70%。 Comparative Example 1 is an example in which the thickness of Sn plating at the time of plating is less than 0.5 μm. The thickness of the Sn layer after reflow is less than 0.2 μm, the area ratio of the Cu-Sn alloy layer exposed to the outermost surface is more than 40%, the Ra in the direction perpendicular to the rolling is more than 0.05 μm, and the specular reflectance is less than 70%.
比較例2係鍍敷時之Cu基底鍍敷厚度超過0.5μm之例。露出至最表面之Cu-Sn合金層之結晶粒徑超過3μm，壓延直角方向之Ra超過0.05μm，鏡面反射率未達70%。 Comparative Example 2 is an example in which the thickness of the Cu substrate plating during plating is more than 0.5 μm. The crystal grain size of the Cu-Sn alloy layer exposed to the outermost surface exceeds 3 μm, the Ra in the direction perpendicular to the rolling is more than 0.05 μm, and the specular reflectance is less than 70%.
比較例3係回流焊處理之爐溫超過600℃之例，比較例4係回流焊處理之加熱時間超過30秒之例。兩者之回流焊後之Sn層厚度均未達0.2μm，露出至最表面之Cu-Sn合金層之面積率均超過40%，結晶粒徑均超過3μm，壓延直角方向之Ra均超過0.05μm，鏡面反射率均未達70%。 Comparative Example 3 is an example in which the furnace temperature of the reflow process exceeds 600 ° C, and Comparative Example 4 is an example in which the heating time of the reflow process exceeds 30 seconds. The thickness of the Sn layer after reflow soldering is less than 0.2μm, the area ratio of the Cu-Sn alloy layer exposed to the outermost surface is more than 40%, the crystal grain size is more than 3μm, and the Ra in the right angle direction of the rolling exceeds 0.05μm. The specular reflectance is less than 70%.
比較例5及6係未實施霧狀之水冷，且Cu-Sn合金層未露出至最表面之例。均未見放射狀之Sn凝固組織，而Sn粉之產生顯著。 Comparative Examples 5 and 6 were not subjected to water cooling in a mist form, and the Cu-Sn alloy layer was not exposed to the outermost surface. No radial Sn solidification structure was observed, and Sn powder production was remarkable.
比較例7係未實施霧狀之水冷，且Cu-Sn合金層僅稍微露出至最表面之例。未見放射狀之Sn凝固組織，且壓延直角方向之Ra超過0.05μm，鏡面反射率未達70%，Sn粉之產生顯著。 In Comparative Example 7, the water-cooling in the form of a mist was not carried out, and the Cu-Sn alloy layer was only slightly exposed to the outermost surface. No radial Sn solidification structure was observed, and Ra in the direction perpendicular to the rolling direction exceeded 0.05 μm, and the specular reflectance was less than 70%, and the generation of Sn powder was remarkable.
比較例8~11係未實施霧狀之水冷，且Cu-Sn合金層大量露出至最表面之例。由於Cu-Sn合金層露出，因此，Sn粉之產生得到抑制， 但未見放射狀之Sn凝固組織，壓延直角方向之Ra超過0.05μm，鏡面反射率未達70%。即，無法兼具對Sn粉之產生之抑制與良好之表面光澤。 In Comparative Examples 8 to 11, the water-cooling in the form of a mist was not performed, and the Cu-Sn alloy layer was exposed to the outermost surface in a large amount. Since the Cu-Sn alloy layer is exposed, the generation of Sn powder is suppressed, However, no radial Sn solidified structure was observed, and the Ra in the direction perpendicular to the rolling was more than 0.05 μm, and the specular reflectance was less than 70%. That is, it is impossible to combine the suppression of the generation of Sn powder with a good surface gloss.
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