WO2012133378A1 - Matériau d'étamage - Google Patents

Matériau d'étamage Download PDF

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Publication number
WO2012133378A1
WO2012133378A1 PCT/JP2012/057877 JP2012057877W WO2012133378A1 WO 2012133378 A1 WO2012133378 A1 WO 2012133378A1 JP 2012057877 W JP2012057877 W JP 2012057877W WO 2012133378 A1 WO2012133378 A1 WO 2012133378A1
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WO
WIPO (PCT)
Prior art keywords
plating
copper
layer
alloy
exposed
Prior art date
Application number
PCT/JP2012/057877
Other languages
English (en)
Japanese (ja)
Inventor
原田　宏司
慶太郎 金濱
Original Assignee
Jx日鉱日石金属株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jx日鉱日石金属株式会社 filed Critical Jx日鉱日石金属株式会社
Priority to KR1020137024130A priority Critical patent/KR101457321B1/ko
Priority to CN201280016466.XA priority patent/CN103459678B/zh
Publication of WO2012133378A1 publication Critical patent/WO2012133378A1/fr

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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
    • 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
    • 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
    • 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • 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
    • 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

Definitions

  • the present invention relates to a Sn plating material which is suitable as a conductive spring material for connectors, terminals, relays, switches and the like, and which has a Sn plating layer obtained by performing a reflow treatment on the surface of copper or a copper alloy strip.
  • Sn plating is given (patent document 1).
  • a reflow process is performed by heating to a melting point of Sn or higher to improve adhesion and appearance.
  • this invention is made
  • the present inventors have found that when the Cu—Sn alloy layer is partially exposed on the outermost surface after the reflow treatment of the plating layer on the surface of the copper or copper alloy strip, the exposed Cu—Sn alloy layer becomes the outermost surface. It was found that the pure Sn layer was retained (pinned) and the generation of Sn powder was suppressed. That is, the Sn plating material of the present invention is an Sn plating material having an Sn plating layer obtained by performing reflow treatment on the surface of copper or a copper alloy strip, and the area ratio of the Cu—Sn alloy layer exposed on the outermost surface is 0. The number of the exposed Cu—Sn alloy layers is 100 to 900 per 0.033 mm 2 when viewed from the outermost surface.
  • the exposed Cu—Sn alloy layer holds the pure Sn layer on the outermost surface ( Pinning) and the generation of Sn powder can be suppressed.
  • % means “% by mass” unless otherwise specified.
  • composition of base material As the copper strip used as the base material of the Sn plating material, tough pitch copper and oxygen-free copper having a purity of 99.9% or more can be used, and the required strength as a copper alloy strip.
  • a known copper alloy can be used depending on the conductivity. Examples of known copper alloys include phosphor bronze, brass, titanium copper, and Corson alloy.
  • Sn plating layer An Sn plating layer subjected to reflow treatment is formed on the surface of the copper or copper alloy strip.
  • the Sn plating layer is plated directly on the surface of the copper or copper alloy strip, or is plated through a base plating.
  • the base plating include Ni and Cu. One of these may be plated, or both may be plated in the order of Ni and Cu to form a Cu / Ni two-layer base plating.
  • the Sn plating material according to the embodiment of the present invention is generally a base plating layer by electroplating after degreasing and pickling the surface of a copper or copper alloy strip as a base material in a continuous plating line.
  • a Sn layer is formed by a known electroplating method, and finally a reflow process is performed to melt the Sn layer.
  • Sn plating can be performed by a well-known method, for example, a sulfuric acid bath, a sulfonic acid bath, a halogen bath etc. can be used.
  • Cu-Sn alloy layer When reflow treatment is performed on the surface of the base material (copper or copper alloy strip) 2 after Sn plating, Cu in the base material (copper or copper alloy strip) 2 is applied to the surface Sn plating layer 6 as shown in FIG.
  • the Cu—Sn alloy layer 4 is formed between the Sn plating layer 6 and the base material.
  • the Cu—Sn alloy layer 4 usually has a composition of Cu 6 Sn 5 and / or Cu 3 Sn 4 , but the above-described base plating components and additive elements when the base material is a copper alloy May be included.
  • pure Sn is completely left on the outermost surface so that the Cu—Sn alloy layer 4 is not exposed on the surface, but in the present invention, 0.5 to 4 is applied to the outermost surface.
  • the Cu—Sn alloy layer is exposed at an area ratio of%. Since the Cu—Sn alloy layer is harder than pure Sn, the scratches 21 generated when the outermost surface is held by the pad during press working are stopped by the exposed Cu—Sn alloy layer 4a, and the scratches 21 are elongated to cause pure Sn on the surface. Peeling (Sn powder) is suppressed.
  • the area ratio of the Cu—Sn alloy layer exposed on the outermost surface is set to 0.5 to 4%.
  • the area ratio is less than 0.5%, the pinning effect described above by the Cu—Sn alloy layer does not occur.
  • the area ratio exceeds 4% the amount of pure Sn on the surface is reduced, solder wettability, corrosion resistance, electrical connectivity, and the like are deteriorated, and the surface is crumpled and the appearance is inferior.
  • SEM scanning electron microscope
  • the area of the Cu—Sn alloy layer is obtained. It can be calculated. (Binarization is set to 120 in the luminance range 255 of the SEM device, for example)
  • As a method for managing the area ratio of the Cu—Sn alloy layer to 0.5 to 4% adjustment of the reflow temperature and reflow time and adjustment of the Sn plating thickness can be mentioned. By adjusting these, the degree of growth of the Cu—Sn alloy layer from the base material side to the surface can be controlled, and the ratio of the Cu—Sn alloy layer reaching (exposed) the outermost surface can be controlled.
  • the thickness of the Sn layer before the reflow process can be 0.1 to 5.0 ⁇ m
  • the thickness of the pure Sn layer after the reflow process can also be 0.1 to 4.5 ⁇ m.
  • the number of exposed Cu—Sn alloy layers is preferably 100 to 900 per 0.033 mm 2 . More preferably, the number of exposed Cu—Sn alloy layers is 200 to 900.
  • Simply defining the area ratio of the Cu—Sn alloy layer exposed on the outermost surface includes, for example, a case where a small number of coarse Cu—Sn alloy layers are exposed. In this case, the pinning effect is It is less likely to occur, and it is better that a large number of Cu—Sn alloy layers are dispersed on the outermost surface even with the same area ratio. Therefore, the number of Cu—Sn alloy layers is defined.
  • the number of the exposed Cu—Sn alloy layers can be obtained by counting the number of white images obtained by binarizing the reflected electron image described above with computer software.
  • the base Ni plating was electroplated with a sulfuric acid bath (liquid temperature: about 50 ° C., current density: 5 A / dm 2 ), and the thickness of the base Ni plating was 0.3 ⁇ m.
  • the base Cu plating was electroplated with a sulfuric acid bath (liquid temperature about 50 ° C., current density 30 A / dm 2 ), and the thickness of the base Cu plating was 0.5 ⁇ m.
  • Sn plating was electroplated with a phenol sulfonic acid bath (liquid temperature: about 35 ° C., current density: 20 A / dm 2 ), and the thickness of the Sn plating was 1.2 ⁇ m. The thickness of each plating layer was measured with an electrolytic film thickness meter.
  • each sample was placed in a heating furnace with a melting point of 7% to melt the Sn layer, and then cooled through a cooling bath with a liquid temperature of 60 ° C. to obtain a final product with a reflow treatment on the surface. .
  • Tables 1 to 5 the temperature of the heating furnace and the frequency of the fan that blows hot air from the heating furnace to the sample were changed. The higher the temperature of the heating furnace and the fan frequency, the better the sample is heated and the Cu—Sn alloy layer grows. Further, when the fan frequency is increased, the nucleation of the Cu—Sn alloy layer is promoted by the action of the wind blown on the material surface, and the particle size of the Cu—Sn alloy layer is reduced.
  • the area ratio of the Cu—Sn alloy layer exposed on the outermost surface is 0.5 to 4%, and the number of exposed Cu—Sn alloy layers as viewed from the outermost surface is In each Example, which was 100 to 900 per 0.033 mm 2 , the generation of Sn powder was small and the solder wettability was excellent.
  • the area ratio of the Cu—Sn alloy layer exposed on the outermost surface was less than 0.5%, and Comparative Examples 9, 10, 12, 26, 27, 29, 43, 44, 46, 54, 59, 64, 69,74,79,84,89,95,99,104,109,114,119,124,129,134,139,144,149,154,159,164,169,174,179,184,189, In the case of 195, 200, 204, 209, a lot of Sn powder was generated.
  • the area ratio of the Cu—Sn alloy layer exposed on the outermost surface was 0.5% to 4%, the number of Cu—Sn alloy layers exposed on the outermost surface exceeded 900, Comparative Example 11 , 28, 45, 75, 94, 100, 115, 130, 135, 160, 165, 185, 190, 194, and 199, Sn powder generation was small, but solder wettability was poor. Further, although the area ratio of the Cu—Sn alloy layer exposed on the outermost surface was 0.5% to 4%, the number of Cu—Sn alloy layers exposed on the outermost surface was less than 100, Comparative Example 106 , 110 and 211, a lot of Sn powder was generated.
  • FIG. 2A is a SEM image (reflection electron image) of the surface of Example 1, and FIG. 2B is a binarized image thereof.
  • Base material (copper or copper alloy strip) 4 Cu—Sn alloy layer 4 a Cu—Sn alloy layer exposed on the outermost surface 6 Sn plating layer subjected to reflow treatment 10 Sn plating material 21 Scratch

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

[Problème] L'invention a pour but de concevoir un matériau d'étamage qui permet de supprimer la présence de poudre d'étain en exposant partiellement une couche d'alliage Cu-Sn dans une couche d'étamage soumise à une refusion sur la surface d'une bande de cuivre ou d'alliage de cuivre. [Solution] Ledit matériau d'étamage (10) comporte une couche d'étamage (6) pour laquelle un traitement de refusion a été réalisé sur la surface d'une bande de cuivre ou d'alliage de cuivre (2). La proportion surfacique d'une couche d'alliage Cu-Sn (4a) exposée sur la surface extérieure est de 0,5-4 %, et vus depuis la surface extérieure, le nombre de points exposés pour cette couche d'alliage Cu-Sn est de 100-900 pour 0,033 mm2.
PCT/JP2012/057877 2011-03-31 2012-03-27 Matériau d'étamage WO2012133378A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020137024130A KR101457321B1 (ko) 2011-03-31 2012-03-27 Sn 도금재
CN201280016466.XA CN103459678B (zh) 2011-03-31 2012-03-27 镀锡材料

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011080394 2011-03-31
JP2011-080394 2011-03-31
JP2011086947A JP5389097B2 (ja) 2011-03-31 2011-04-11 Ｓｎめっき材
JP2011-086947 2011-04-11

Publications (1)

Publication Number Publication Date
WO2012133378A1 true WO2012133378A1 (fr) 2012-10-04

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PCT/JP2012/057877 WO2012133378A1 (fr) 2011-03-31 2012-03-27 Matériau d'étamage

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JP (1) JP5389097B2 (fr)
KR (1) KR101457321B1 (fr)
CN (1) CN103459678B (fr)
WO (1) WO2012133378A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5587935B2 (ja) * 2012-03-30 2014-09-10 Ｊｘ日鉱日石金属株式会社 Ｓｎめっき材
JP2015225704A (ja) * 2014-05-26 2015-12-14 矢崎総業株式会社 端子
JP7226210B2 (ja) * 2019-09-19 2023-02-21 株式会社オートネットワーク技術研究所 ピン端子、コネクタ、コネクタ付きワイヤーハーネス、及びコントロールユニット

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3378717B2 (ja) * 1995-01-19 2003-02-17 古河電気工業株式会社 リフローめっき部材の製造方法
JP2006077307A (ja) * 2004-09-10 2006-03-23 Kobe Steel Ltd 接続部品用導電材料及びその製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5614328A (en) * 1995-01-19 1997-03-25 The Furukawa Electric Co. Ltd. Reflow-plated member and a manufacturing method therefor
JP4308931B2 (ja) * 1997-11-04 2009-08-05 三菱伸銅株式会社 ＳｎまたはＳｎ合金メッキ銅合金薄板およびその薄板で製造したコネクタ
JP2006283149A (ja) * 2005-04-01 2006-10-19 Nikko Kinzoku Kk 銅又は銅合金の表面処理方法、表面処理材及びこれを用いた電子部品

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3378717B2 (ja) * 1995-01-19 2003-02-17 古河電気工業株式会社 リフローめっき部材の製造方法
JP2006077307A (ja) * 2004-09-10 2006-03-23 Kobe Steel Ltd 接続部品用導電材料及びその製造方法

Also Published As

Publication number Publication date
KR101457321B1 (ko) 2014-11-05
CN103459678A (zh) 2013-12-18
JP5389097B2 (ja) 2014-01-15
CN103459678B (zh) 2016-04-13
KR20130124384A (ko) 2013-11-13
JP2012214864A (ja) 2012-11-08

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