JP7014695B2 - Conductive materials, molded products and electronic components - Google Patents

Conductive materials, molded products and electronic components Download PDF

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JP7014695B2
JP7014695B2 JP2018196983A JP2018196983A JP7014695B2 JP 7014695 B2 JP7014695 B2 JP 7014695B2 JP 2018196983 A JP2018196983 A JP 2018196983A JP 2018196983 A JP2018196983 A JP 2018196983A JP 7014695 B2 JP7014695 B2 JP 7014695B2
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conductive material
plating
plating layer
resin
alloy
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JP2020063492A (en
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康則 佐々木
高広 川村
良聡 小林
玲宏 相場
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JX Nippon Mining and Metals Corp
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Priority to PCT/JP2019/028332 priority patent/WO2020079904A1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • 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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • 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
    • 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
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline 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
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/495—Lead-frames or other flat leads
    • H01L23/49579—Lead-frames or other flat leads characterised by the materials of the lead frames or layers thereon
    • H01L23/49582—Metallic layers on lead frames
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/50—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor for integrated circuit devices, e.g. power bus, number of leads

Description

本発明は、導電性材料、成型品及び電子部品に関する。 The present invention relates to conductive materials, molded products and electronic components.

近年、金属と樹脂との密着性の改善要望が増加している。例えば、リードフレーム、バズバーモジュール等のような金属製の電子部品を衝撃、温度、湿度等の要因から守るために、当該電子部品の表面を樹脂で固める樹脂成型、樹脂封止、または、モールド成型等を施すことがある。このような場合、使用中に樹脂が剥離しないように当該電子部品の金属表面と樹脂とが優れた密着力で密着されている必要がある。特に、車載向けについては過酷な環境下にあるエンジンルーム周りでの電子化が進むことで、より一層の密着性の向上が求められている。 In recent years, there has been an increasing demand for improving the adhesion between metal and resin. For example, in order to protect metal electronic components such as lead frames and buzz bar modules from factors such as impact, temperature, and humidity, resin molding, resin encapsulation, or molding is performed by solidifying the surface of the electronic components with resin. It may be molded. In such a case, it is necessary that the metal surface of the electronic component and the resin are in close contact with each other with excellent adhesion so that the resin does not peel off during use. In particular, for in-vehicle use, further improvement in adhesion is required due to the progress of digitization around the engine room in a harsh environment.

金属と樹脂との密着性の向上を図った公知技術として特許文献１～３には、樹脂封止型半導体装置におけるリードフレームとモールド樹脂との密着性を高めるために、リードフレームのメッキ表面を粗化する技術が提案されている。 As a known technique for improving the adhesion between the metal and the resin, Patent Documents 1 to 3 describe the plated surface of the lead frame in order to improve the adhesion between the lead frame and the mold resin in the resin-sealed semiconductor device. A roughening technique has been proposed.

また、最近の公知技術として特許文献４には、金属と樹脂との密着性の向上を図るために比表面積及び表層の酸化膜厚に着目した技術が提案されている。 Further, as a recently known technique, Patent Document 4 proposes a technique focusing on the specific surface area and the oxide film thickness of the surface layer in order to improve the adhesion between the metal and the resin.

特開平６－２９４３９号公報Japanese Unexamined Patent Publication No. 6-29439 特開平１０－２７８７３号公報Japanese Unexamined Patent Publication No. 10-27873 特開２００６－９３５５９号公報Japanese Unexamined Patent Publication No. 2006-93559 国際公開第２０１７／１７９４４７号International Publication No. 2017/179447

従来、高温高湿試験において例えばＪＥＤＥＣ－ＬＥＶＥＬ１等をクリアすることが求められてきたが、近年では自動車の電子化等によって、さらに過酷な環境下、例えばヒートサイクル試験等において耐久性を有することが要求されており、従来の技術では必ずしも特性が十分とはいえない状況が散見されている。 Conventionally, it has been required to clear, for example, JEDEC-LEVEL1 in a high temperature and high humidity test, but in recent years, due to the digitization of automobiles, it is possible to have durability in a harsher environment such as a heat cycle test. There are some situations where the characteristics are not always sufficient with the conventional technology.

本発明は上記の課題を解決するためになされたものであり、過酷な環境下においても優れた樹脂密着性を示す導電性材料を提供する。 The present invention has been made to solve the above problems, and provides a conductive material that exhibits excellent resin adhesion even in a harsh environment.

本発明者らは、鋭意検討の結果、樹脂を成型するまたは樹脂で封止する表面を金属で構成し、当該表面を所定の形態に制御することで、当該課題を解決し得る導電性材料が得られることを見出した。 As a result of diligent studies, the present inventors have found a conductive material that can solve the problem by forming the surface of the resin to be molded or sealed with the metal with a metal and controlling the surface to a predetermined form. I found that I could get it.

以上の知見を基礎として完成した本発明は一実施形態において、表面に樹脂を成型する、または、表面を樹脂で封止する導電性材料であって、
前記表面が金属で構成され、下記（１）及び（２）の条件を満たす導電性材料である。
（１）算術平均面粗さ高さＳａが０．２５～０．４μｍ、
（２）山の頂点密度Ｓｐｄが１ｍｍ2あたり２５０万個以上。 The present invention completed based on the above findings is, in one embodiment, a conductive material in which a resin is molded on the surface or the surface is sealed with the resin.
The surface is made of metal and is a conductive material satisfying the following conditions (1) and (2).
(1) Arithmetic mean surface roughness height Sa is 0.25 to 0.4 μm,
(2) The peak density Spd of the mountain is 2.5 million or more per 1 mm 2 .

本発明の導電性材料は更に別の一実施形態において、前記表面の最大面粗さ高さＳｚが３．５～６．５μｍである。 In still another embodiment, the conductive material of the present invention has a maximum surface roughness height Sz of 3.5 to 6.5 μm.

本発明の導電性材料は更に別の一実施形態において、前記導電性材料が基材と前記基材上に形成されためっき層とを含み、前記表面が前記めっき層である。 In still another embodiment, the conductive material of the present invention includes a base material and a plating layer formed on the base material, and the surface thereof is the plating layer.

本発明の導電性材料は更に別の一実施形態において、前記基材が、銅、銅合金、アルミニウム、アルミニウム合金、鉄及び鉄合金のいずれかで構成されている。 In still another embodiment of the conductive material of the present invention, the base material is made of any one of copper, a copper alloy, aluminum, an aluminum alloy, iron and an iron alloy.

本発明の導電性材料は更に別の一実施形態において、前記めっき層が１種以上のめっき層で構成されている。 In still another embodiment, the conductive material of the present invention is composed of one or more types of plating layers.

本発明の導電性材料は更に別の一実施形態において、前記めっき層は前記基材上に形成された第１めっき層を有し、前記第１めっき層が銅、銅合金、ニッケル及びニッケル合金のいずれかで構成されている。 In still another embodiment, the conductive material of the present invention has a first plating layer formed on the substrate, and the first plating layer is a copper, copper alloy, nickel and nickel alloy. It is composed of any of.

本発明の導電性材料は更に別の一実施形態において、前記めっき層は前記第１めっき層上に形成された第２めっき層を有し、前記第２めっき層がパラジウム、パラジウム合金、金及び金合金のいずれかで構成されている。 In still another embodiment, the conductive material of the present invention has a second plating layer formed on the first plating layer, and the second plating layer is palladium, a palladium alloy, gold and the like. It is composed of any of the gold alloys.

本発明の導電性材料は更に別の一実施形態において、前記１種以上のめっき層で構成された前記めっき層の厚みの総和が１～７μｍである。 In still another embodiment, the conductive material of the present invention has a total thickness of 1 to 7 μm of the plating layer composed of the one or more types of plating layers.

本発明の導電性材料は更に別の一実施形態において、前記（１）及び（２）の条件を満たす表面を部分的に有する。 In still another embodiment, the conductive material of the present invention partially has a surface satisfying the above conditions (1) and (2).

本発明は更に別の一実施形態において、前記表面に樹脂が成型された、または、前記表面が樹脂で封止された本発明の導電性材料を備えた成型品である。 In still another embodiment, the present invention is a molded product provided with the conductive material of the present invention, wherein the surface is molded with a resin or the surface is sealed with a resin.

本発明は更に別の一実施形態において、本発明の導電性材料を備えた電子部品である。 The present invention is, in yet another embodiment, an electronic component comprising the conductive material of the present invention.

本発明によれば、過酷な環境下においても優れた樹脂密着性を示す導電性材料を提供することができる。 According to the present invention, it is possible to provide a conductive material that exhibits excellent resin adhesion even in a harsh environment.

実施形態１に係る導電性材料の構成を示す断面模式図である。It is sectional drawing which shows the structure of the conductive material which concerns on Embodiment 1. FIG. 実施形態２に係る導電性材料の構成を示す断面模式図である。It is sectional drawing which shows the structure of the conductive material which concerns on Embodiment 2. 実施形態３に係る導電性材料の構成を示す断面模式図である。It is sectional drawing which shows the structure of the conductive material which concerns on Embodiment 3. FIG.

＜導電性材料＞
本発明の実施形態に係る導電性材料は、表面に樹脂を成型する、または、表面を樹脂で封止する導電性材料であって、表面が金属で構成され、下記（１）及び（２）の条件を満たす。
（１）算術平均面粗さ高さＳａが０．２５～０．４μｍ、
（２）山の頂点密度Ｓｐｄが１ｍｍ2あたり２５０万個以上。 <Conductive material>
The conductive material according to the embodiment of the present invention is a conductive material in which a resin is molded on the surface or the surface is sealed with a resin, the surface of which is made of metal, and the following (1) and (2). Satisfy the conditions.
(1) Arithmetic mean surface roughness height Sa is 0.25 to 0.4 μm,
(2) The peak density Spd of the mountain is 2.5 million or more per 1 mm 2 .

従来、金属と樹脂との密着性について、金属の線粗さ（Ｒｚ，Ｒａ）を制御していたものの、より過酷な環境下で使用される電子部品での樹脂との密着性を制御するパラメータとしては不十分である。これに対し、詳細は後述するが、本発明では面における粗さとして、国際標準化機構ＩＳＯ２５１７８－２：２０１２に規定されるＳａ、Ｓｐｄを導入することにより、従来よりも良好に樹脂との密着性を制御することができるようになった。 Conventionally, regarding the adhesion between metal and resin, the line roughness (Rz, Ra) of the metal was controlled, but the parameter that controls the adhesion with resin in electronic parts used in more harsh environments. Is not enough. On the other hand, although the details will be described later, in the present invention, by introducing Sa and Spd specified in the International Organization for Standardization ISO25178-2: 2012 as the roughness on the surface, the adhesion to the resin is better than before. Can now be controlled.

本発明の実施形態に係る導電性材料は少なくとも表面が金属で構成されていればよいため、詳細は後述するが、１種類の金属材料で形成してもよく、基材と表面の金属層とに分けて形成してもよい。 Since the conductive material according to the embodiment of the present invention may be formed of one kind of metal material, the details may be described later because at least the surface thereof may be made of metal. It may be formed separately into.

本発明の実施形態に係る導電性材料の表面の算術平均面粗さ高さＳａは０．２５～０．４μｍに制御されている。導電性材料の表面のＳａが０．２５μｍ未満であると表面の粗化不足によりアンカー効果が不十分となって、樹脂との密着性が低下する。導電性材料の表面のＳａが０．４μｍ超であると、導電性材料の表面の粗化されて生じた先端部分が破断しやすくなる。導電性材料の表面のＳａは、０．２７～０．３８μｍであるのが好ましく、０．３～０．３５μｍであるのがより好ましい。 The arithmetic mean surface roughness height Sa of the surface of the conductive material according to the embodiment of the present invention is controlled to 0.25 to 0.4 μm. If the Sa of the surface of the conductive material is less than 0.25 μm, the anchor effect becomes insufficient due to insufficient roughening of the surface, and the adhesion to the resin is lowered. When Sa on the surface of the conductive material is more than 0.4 μm, the tip portion formed by roughening the surface of the conductive material is likely to break. The Sa on the surface of the conductive material is preferably 0.27 to 0.38 μm, more preferably 0.3 to 0.35 μm.

本発明の実施形態に係る導電性材料の金属表面と樹脂とが密着するとき、樹脂の方が金属より熱膨張係数が大きいため、樹脂の熱膨張を金属アンカーによって抑制する必要がある。本発明では当該樹脂との熱膨張係数差の問題に対し、導電性材料の表面の山の頂点密度Ｓｐｄが１ｍｍ2あたり２５０万個以上に制御されている。導電性材料の表面のＳｐｄが１ｍｍ2あたり２５０万個未満であると、当該アンカー効果が不十分となり、熱膨張係数差に負けて、樹脂との剥離が生じるおそれがある。また、導電性材料の表面のＳｐｄは大きすぎると、アンカー密度が高くなりすぎて、アンカー間の隙間に樹脂が入り込みにくくなり、却って密着強度が低下するおそれが生じる場合がある。このような観点から、導電性材料の表面のＳｐｄは、前記Ｓａとの組合せで効果を発揮するため特に上限は設けないが、１ｍｍ2あたり５５０万個以下であるのが好ましい。また、導電性材料の表面のＳｐｄは、１ｍｍ2あたり２６０～６００万個であるのが好ましく、１ｍｍ2あたり３００～５５０万個であるのがより好ましい。 When the metal surface of the conductive material according to the embodiment of the present invention is in close contact with the resin, the coefficient of thermal expansion of the resin is larger than that of the metal, so that it is necessary to suppress the thermal expansion of the resin by a metal anchor. In the present invention, the peak density Spd of the surface of the conductive material is controlled to 2.5 million or more per 1 mm 2 to solve the problem of the difference in the coefficient of thermal expansion from the resin. If the Spd on the surface of the conductive material is less than 2.5 million pieces per 1 mm 2 , the anchor effect becomes insufficient, and the difference in the coefficient of thermal expansion may be lost and peeling from the resin may occur. Further, if the Spd on the surface of the conductive material is too large, the anchor density becomes too high, and it becomes difficult for the resin to enter the gap between the anchors, which may lead to a decrease in the adhesion strength. From such a viewpoint, the Spd on the surface of the conductive material is not particularly limited because it exerts an effect in combination with the Sa, but it is preferably 5.5 million or less per 1 mm 2 . Further, the Spd on the surface of the conductive material is preferably 2.6 to 6 million pieces per 1 mm 2 , and more preferably 3 to 5.5 million pieces per 1 mm 2 .

本発明の実施形態に係る導電性材料の表面の最大面粗さ高さＳｚ（ＩＳＯ２５１７８－２：２０１２）は３．５～６．５μｍであるのが好ましい。導電性材料の表面のＳｚが３．５μｍ未満であると表面の粗化不足によりアンカー効果が不十分となって、樹脂との密着性が低下する。導電性材料の表面のＳｚが６．５μｍ超であると、導電性材料の表面の高低間の隙間に樹脂が入り込みにくくなるおそれがある。導電性材料の表面のＳａは、３．７～６．０μｍであるのが好ましく、４．５～５．０μｍであるのがより好ましい。 The maximum surface roughness height Sz (ISO25178-2: 2012) of the surface of the conductive material according to the embodiment of the present invention is preferably 3.5 to 6.5 μm. If the Sz on the surface of the conductive material is less than 3.5 μm, the anchor effect becomes insufficient due to insufficient roughening of the surface, and the adhesion to the resin is lowered. If the Sz on the surface of the conductive material is more than 6.5 μm, it may be difficult for the resin to enter the gap between the heights of the surface of the conductive material. The Sa on the surface of the conductive material is preferably 3.7 to 6.0 μm, more preferably 4.5 to 5.0 μm.

本発明の実施形態に係る導電性材料は、表面が少なくとも金属であればよく、特に限定されないが、以下の３パターンの形態（実施形態１～３）を含む。 The conductive material according to the embodiment of the present invention is not particularly limited as long as the surface is at least metal, and includes the following three patterns (embodiments 1 to 3).

・導電性材料の構成に係る実施形態１
図１は、本発明の実施形態１に係る導電性材料１０の構成を示す断面模式図である。導電性材料１０は金属材料で構成されており、上記（１）及び（２）の条件を満たす表面１１を有する。図１の点線枠１２部分の拡大図が右図に示されている。なお図１の右図は導電性材料１０の粗化表面の一例を示すものであり、このような形状の粗化表面に限定されるものではない。このような構成によれば、導電性材料を構成する材料が１種類の金属材料であるため、製造効率または製造コストが良好となる。導電性材料１０の金属材料としては、例えば銅、銅合金、アルミニウム、アルミニウム合金、鉄、鉄合金、ニッケル、ニッケル合金、パラジウム、パラジウム合金、金及び金合金のいずれかで構成することができる。また、金属と樹脂とでは、樹脂の方が熱膨張係数が大きい。このとき、樹脂に密着する金属（導電性材料１０の金属材料）の熱伝導率が高ければ、樹脂に籠っている熱を効率的に逃がすことができる。その結果、樹脂の熱膨張を抑えることができる。このような観点から、導電性材料１０の金属材料の熱伝導率に比例する導電率は、１０％ＩＡＣＳ以上であることが好ましい。 Embodiment 1 relating to the composition of a conductive material
FIG. 1 is a schematic cross-sectional view showing the structure of the conductive material 10 according to the first embodiment of the present invention. The conductive material 10 is made of a metal material and has a surface 11 that satisfies the above conditions (1) and (2). An enlarged view of the dotted frame 12 portion of FIG. 1 is shown in the right figure. The right figure of FIG. 1 shows an example of the roughened surface of the conductive material 10, and is not limited to the roughened surface having such a shape. According to such a configuration, since the material constituting the conductive material is one kind of metal material, the manufacturing efficiency or the manufacturing cost is good. The metal material of the conductive material 10 can be made of, for example, copper, copper alloy, aluminum, aluminum alloy, iron, iron alloy, nickel, nickel alloy, palladium, palladium alloy, gold or gold alloy. Further, among the metal and the resin, the resin has a larger coefficient of thermal expansion. At this time, if the thermal conductivity of the metal (metal material of the conductive material 10) that adheres to the resin is high, the heat trapped in the resin can be efficiently dissipated. As a result, the thermal expansion of the resin can be suppressed. From this point of view, the conductivity proportional to the thermal conductivity of the metallic material of the conductive material 10 is preferably 10% IACS or more.

導電性材料１０は、所定の金属材料を準備し、当該金属材料の表面に、エッチング処理、ブラスト処理、または、凹凸面を有する圧延ロールによる転写処理を施すことで、上記（１）及び（２）の条件を満たす表面１１を形成することができる。エッチング処理としては、例えば、メック株式会社製 ＣＺ８１０１（製品名）や三菱ガス化学株式会社製 ＣＰＥ９００（製品名）、さらにメック株式会社製 ＮＲ１８７０（製品名）など、各社より市販されているエッチング液を使用して所定の形状に制御することができる。なおエッチング方法としては、浸漬式、スプレー式、電解式など、さまざまな手法を採用することができる。 For the conductive material 10, a predetermined metal material is prepared, and the surface of the metal material is subjected to an etching treatment, a blast treatment, or a transfer treatment using a rolling roll having an uneven surface, whereby (1) and (2) above. ) Satisfy the condition of). As the etching treatment, for example, an etching solution commercially available from each company such as CZ8101 (product name) manufactured by MEC Co., Ltd., CPE900 (product name) manufactured by Mitsubishi Gas Chemical Company Ltd., and NR1870 (product name) manufactured by MEC COMPANY Ltd. is used. It can be used to control a predetermined shape. As the etching method, various methods such as an immersion type, a spray type, and an electrolytic type can be adopted.

・導電性材料の構成に係る実施形態２
図２は、本発明の実施形態２に係る導電性材料２０の構成を示す断面模式図である。導電性材料２０は、基材２２と基材２２上に形成されためっき層２３とを含み、上記（１）及び（２）の条件を満たす表面２１がめっき層２３である。図２の点線枠２４部分の拡大図が右図に示されている。なお図２の右図は導電性材料２０の粗化表面の一例を示すものであり、このような形状の粗化表面に限定されるものではない。このような構成によれば、上記（１）及び（２）の条件を満たす表面をめっき層で制御することができ、当該表面（表層、すなわちめっき層）の厚みを容易に制御することができる。 Embodiment 2 relating to the composition of a conductive material
FIG. 2 is a schematic cross-sectional view showing the structure of the conductive material 20 according to the second embodiment of the present invention. The conductive material 20 includes a base material 22 and a plating layer 23 formed on the base material 22, and the surface 21 satisfying the above conditions (1) and (2) is the plating layer 23. An enlarged view of the dotted frame 24 portion of FIG. 2 is shown in the right figure. The right figure of FIG. 2 shows an example of the roughened surface of the conductive material 20, and is not limited to the roughened surface having such a shape. According to such a configuration, the surface satisfying the above conditions (1) and (2) can be controlled by the plating layer, and the thickness of the surface (surface layer, that is, the plating layer) can be easily controlled. ..

基材２２は樹脂で構成されていてもよく、銅、銅合金、アルミニウム、アルミニウム合金、鉄及び鉄合金のいずれかの金属で構成されていてもよい。また、基材２２がめっき層２３の金属と同種類の金属で構成されていてもよい。めっき層２３は銅、銅合金、ニッケル及びニッケル合金のいずれかで構成されていてもよい。また、樹脂に間接的に密着する金属（導電性材料２０の基材２２）の熱伝導率が高ければ、樹脂に籠っている熱を効率的に逃がすことができる。その結果、樹脂の熱膨張を抑えることができる。このような観点から、導電性材料２０の基材２２の熱伝導率に比例する導電率は、１０％ＩＡＣＳ以上であることが好ましい。 The base material 22 may be made of a resin, or may be made of any metal such as copper, a copper alloy, aluminum, an aluminum alloy, iron and an iron alloy. Further, the base material 22 may be made of the same type of metal as the metal of the plating layer 23. The plating layer 23 may be made of any one of copper, a copper alloy, nickel and a nickel alloy. Further, if the thermal conductivity of the metal (base material 22 of the conductive material 20) that indirectly adheres to the resin is high, the heat trapped in the resin can be efficiently dissipated. As a result, the thermal expansion of the resin can be suppressed. From such a viewpoint, the conductivity proportional to the thermal conductivity of the base material 22 of the conductive material 20 is preferably 10% IACS or more.

導電性材料２０は、所定の材料で形成された基材２２を準備し、当該基材２２上に所定のめっき条件でめっき層２３を形成する。このとき、めっき浴の組成、めっき温度、電流密度、めっき厚等のめっき条件を制御することで、上記（１）及び（２）の条件を満たす表面２１を形成することができる。 As the conductive material 20, a base material 22 made of a predetermined material is prepared, and a plating layer 23 is formed on the base material 22 under predetermined plating conditions. At this time, by controlling the plating conditions such as the composition of the plating bath, the plating temperature, the current density, and the plating thickness, the surface 21 satisfying the above conditions (1) and (2) can be formed.

・導電性材料の構成に係る実施形態３
図３は、本発明の実施形態３に係る導電性材料３０の構成を示す断面模式図である。導電性材料３０は、基材３２と２種のめっき層（第１めっき層３３、第２めっき層３４）とで構成されている。第１めっき層３３は基材３２上に形成され、第２めっき層３４は第１めっき層３３上に形成されており、上記（１）及び（２）の条件を満たす表面３１が第２めっき層３４である。図３の点線枠３５部分の拡大図が右図に示されている。なお図３の右図は導電性材料３０の粗化表面の一例を示すものであり、このような形状の粗化表面に限定されるものではない。このような構成によれば、上記（１）及び（２）の条件を満たす表面をめっき層で制御することができ、当該表面（表層、すなわちめっき層）の厚みを容易に制御することができる。また、複層のめっき層を良好なコスト及び効率で製造することができる。 Embodiment 3 relating to the composition of a conductive material
FIG. 3 is a schematic cross-sectional view showing the configuration of the conductive material 30 according to the third embodiment of the present invention. The conductive material 30 is composed of a base material 32 and two types of plating layers (first plating layer 33 and second plating layer 34). The first plating layer 33 is formed on the base material 32, the second plating layer 34 is formed on the first plating layer 33, and the surface 31 satisfying the above conditions (1) and (2) is the second plating. Layer 34. An enlarged view of the dotted frame 35 portion of FIG. 3 is shown in the right figure. The right figure of FIG. 3 shows an example of the roughened surface of the conductive material 30, and is not limited to the roughened surface having such a shape. According to such a configuration, the surface satisfying the above conditions (1) and (2) can be controlled by the plating layer, and the thickness of the surface (surface layer, that is, the plating layer) can be easily controlled. .. Further, the multi-layered plating layer can be manufactured at a good cost and efficiency.

基材３２は樹脂で構成されていてもよく、銅、銅合金、アルミニウム、アルミニウム合金、鉄及び鉄合金のいずれかの金属で構成されていてもよい。また、基材３２が第１めっき層３３の金属と同種類の金属で構成されていてもよい。第１めっき層３３は銅、銅合金、ニッケル及びニッケル合金のいずれかで構成されていてもよい。第２めっき層はパラジウム、パラジウム合金、金及び金合金のいずれかで構成されていてもよい。導電性材料３０が例えばリードフレームの場合、第２めっき層の表面（導電性材料３０の最表面）をこのように貴金属めっきにすることによって、半田付け性を高め、且つ、低接触抵抗を実現できる。また、樹脂に間接的に密着する金属（導電性材料３０の基材３２）の熱伝導率が高ければ、樹脂に籠っている熱を効率的に逃がすことができる。その結果、樹脂の熱膨張を抑えることができる。このような観点から、導電性材料３０の基材３２の熱伝導率に比例する導電率は、１０％ＩＡＣＳ以上であることが好ましい。 The base material 32 may be made of a resin, or may be made of any metal such as copper, a copper alloy, aluminum, an aluminum alloy, iron and an iron alloy. Further, the base material 32 may be made of the same type of metal as the metal of the first plating layer 33. The first plating layer 33 may be made of any one of copper, a copper alloy, nickel and a nickel alloy. The second plating layer may be composed of any of palladium, a palladium alloy, gold and a gold alloy. When the conductive material 30 is, for example, a lead frame, the surface of the second plating layer (the outermost surface of the conductive material 30) is plated with a noble metal in this way to improve solderability and realize low contact resistance. can. Further, if the thermal conductivity of the metal (base material 32 of the conductive material 30) that indirectly adheres to the resin is high, the heat trapped in the resin can be efficiently dissipated. As a result, the thermal expansion of the resin can be suppressed. From such a viewpoint, the conductivity proportional to the thermal conductivity of the base material 32 of the conductive material 30 is preferably 10% IACS or more.

導電性材料３０は、所定の材料で形成された基材３２を準備し、当該基材３２上に所定のめっき条件で第１めっき層３３を形成し、続いて第２めっき層３４を形成する。この時、めっき浴の組成、めっき温度、電流密度、めっき厚等のめっき条件を制御することで、上記（１）及び（２）の条件を満たす表面３１を形成することができる。例えば、めっき浴の組成、めっき温度、電流密度、めっき厚等のめっき条件を制御することで上記（１）及び（２）の条件を満たす第１めっき層３３を形成し、このような第１めっき層３３上に薄い第２めっき層３４を形成する。これにより、第２めっき層３４の表面プロフィールは、第１めっき層３３の表面プロフィールと略等しくなる。このようにして、上記（１）及び（２）の条件を満たす表面３１を形成してもよい。 As the conductive material 30, a base material 32 formed of a predetermined material is prepared, a first plating layer 33 is formed on the base material 32 under predetermined plating conditions, and then a second plating layer 34 is formed. .. At this time, by controlling the plating conditions such as the composition of the plating bath, the plating temperature, the current density, and the plating thickness, the surface 31 satisfying the above conditions (1) and (2) can be formed. For example, by controlling the plating conditions such as the composition of the plating bath, the plating temperature, the current density, and the plating thickness, the first plating layer 33 satisfying the above conditions (1) and (2) is formed, and such a first plating layer 33 is formed. A thin second plating layer 34 is formed on the plating layer 33. As a result, the surface profile of the second plating layer 34 becomes substantially equal to the surface profile of the first plating layer 33. In this way, the surface 31 satisfying the above conditions (1) and (2) may be formed.

めっき層は、実施形態２または３のように１層または２層で形成してもよく、３層または４層以上で形成してもよい。また、実施形態１～３の導電性材料１０、２０、３０の最表面は、上記（１）及び（２）の条件を満たしている限り、リン酸エステル系の処理液等による処理を行うことで、めっきの酸化防止剤に係る機能を付与してもよい。また必要に応じて、めっきのピンホールによる腐食を抑制するための封孔処理を付与してもよい。 The plating layer may be formed of one layer or two layers as in the second or third embodiment, or may be formed of three layers or four or more layers. Further, the outermost surfaces of the conductive materials 10, 20 and 30 of the first to third embodiments shall be treated with a phosphoric acid ester-based treatment liquid or the like as long as the above conditions (1) and (2) are satisfied. Then, the function related to the antioxidant of the plating may be imparted. Further, if necessary, a sealing treatment for suppressing corrosion due to plating pinholes may be applied.

本発明の実施形態に係る導電性材料は、１種以上のめっき層で構成されためっき層の厚みの総和が１～７μｍであるのが好ましい。めっき層の厚みの総和が１μｍ未満であると、表面の粗化の形状を十分に形成できず、また基材成分の拡散が進行しやすくなるおそれがある。めっき層の厚みの総和が７μｍ超であると、プレス加工時や曲げ加工時に導電性材料のめっき層にクラックが生じやすくなるおそれがある。 In the conductive material according to the embodiment of the present invention, the total thickness of the plating layers composed of one or more types of plating layers is preferably 1 to 7 μm. If the total thickness of the plating layers is less than 1 μm, the surface roughened shape may not be sufficiently formed, and the diffusion of the base material components may easily proceed. If the total thickness of the plating layers is more than 7 μm, cracks may easily occur in the plating layer of the conductive material during press working or bending.

本発明の実施形態に係る導電性材料は、上記（１）及び（２）の条件を満たす表面を部分的に有してもよい。導電性材料の表面全体が上記（１）及び（２）の条件を満たす場合に対し、当該表面が部分的に設けられていることで、樹脂の密着が不要な部分については容易に樹脂を除去することができる。一例として、当該表面が部分的に設けられていることで、目的箇所から漏れた樹脂（バリ）を容易に除去することができる。また、上記（１）及び（２）の条件を満たすような粗化形状を有する表面は、ワイヤボンディング性が悪化するという特性を有するため、当該表面を部分的に設けることによって、ワイヤボンディング性の悪化を抑制できる。当該部分的に設けられた表面は、ストライプ状であってもよく、スポット状、さらにはリング状などであってもよい。 The conductive material according to the embodiment of the present invention may partially have a surface satisfying the above conditions (1) and (2). When the entire surface of the conductive material satisfies the above conditions (1) and (2), the resin is easily removed from the portion where the resin does not need to be adhered because the surface is partially provided. can do. As an example, since the surface is partially provided, the resin (burr) leaked from the target location can be easily removed. Further, since a surface having a roughened shape that satisfies the above conditions (1) and (2) has a characteristic that the wire bonding property is deteriorated, the wire bonding property can be improved by partially providing the surface. Deterioration can be suppressed. The partially provided surface may be striped, spot-shaped, or even ring-shaped.

＜導電性材料の用途＞
本発明の実施形態に係る導電性材料の用途は特に限定しないが、樹脂との良好な密着性が必要な電子部品の材料として用いることができ、特に、衝撃、温度、湿度等の要因から守るために表面を樹脂で固める樹脂成型、樹脂封止、または、モールド成型等を施す電子部品の材料として用いることができる。当該電子部品としては例えば、リードフレーム、バズバーモジュール等のような金属製の電子部品が挙げられる。本発明の実施形態に係る導電性材料は、このような表面に樹脂成型、樹脂封止、または、モールド成型が施された成型品としても、導電性材料の表面と樹脂との密着性が非常に良好であるため、例えば車載向けのエンジンルーム周りという過酷な環境下で使用される電子部品の材料として用いた場合でも、良好な耐久性が期待できる。 <Use of conductive materials>
The use of the conductive material according to the embodiment of the present invention is not particularly limited, but it can be used as a material for electronic parts that require good adhesion to a resin, and is particularly protected from factors such as impact, temperature, and humidity. Therefore, it can be used as a material for electronic parts to be subjected to resin molding, resin encapsulation, mold molding, etc., in which the surface is hardened with a resin. Examples of the electronic component include metal electronic components such as lead frames and buzz bar modules. The conductive material according to the embodiment of the present invention has a very high adhesion between the surface of the conductive material and the resin even if it is a molded product in which the surface is resin-molded, resin-sealed, or molded. Therefore, good durability can be expected even when used as a material for electronic parts used in a harsh environment such as around an in-vehicle engine room.

以下、本発明の実施例と比較例を共に示すが、これらは本発明をより良く理解するために提供するものであり、本発明が限定されることを意図するものではない。 Hereinafter, both examples and comparative examples of the present invention will be shown, but these are provided for a better understanding of the present invention, and are not intended to limit the present invention.

＜導電性材料の作製＞
実施例１～１４、１７～２１、従来例１、比較例１～２として、表１に示すように基材の表面に表層めっきを形成した。また、実施例１５～１６、従来例２として、表１に示すように基材表面に下地めっき及び表層めっきを形成し、導電性材料の試験片を作製した。各基材の面積は５０ｍｍ×５０ｍｍ、板厚は０．４ｍｍとした。なお、表１に示す基材の種類は以下の通りである。
Ｃ１１０００：９９．９％Ｃｕ
Ｃ１０２００：９９．９％Ｃｕ
Ｃ１９４００：Ｃｕ－２．２％Ｆｅ－０．１５％Ｚｎ－０．０３％Ｐ
Ｃ７０２５０：Ｃｕ－３％Ｎｉ－０．６５％Ｓｉ－０．１５％Ｍｇ
Ａ５０５２：Ａｌ－２．５Ｍｇ－０．４％Ｆｅ－０．２５％Ｓｉ－０．２５％Ｃｒ－０．１％Ｃｕ－０．１％Ｍｎ－０．１％Ｚｎ
４２アロイ：Ｆｅ－４２％Ｎｉ <Manufacturing of conductive material>
As Examples 1 to 14, 17 to 21, Conventional Example 1 and Comparative Examples 1 to 2, surface plating was formed on the surface of the base material as shown in Table 1. Further, as Examples 15 to 16 and Conventional Example 2, as shown in Table 1, base plating and surface plating were formed on the surface of the base material to prepare a test piece of a conductive material. The area of each base material was 50 mm × 50 mm, and the plate thickness was 0.4 mm. The types of base materials shown in Table 1 are as follows.
C11000: 99.9% Cu
C10200: 99.9% Cu
C19400: Cu-2.2% Fe-0.15% Zn-0.03% P
C70250: Cu-3% Ni-0.65% Si-0.15% Mg
A5052: Al-2.5Mg-0.4% Fe-0.25% Si-0.25% Cr-0.1% Cu-0.1% Mn-0.1% Zn
42 Alloy: Fe-42% Ni

各めっきを行う前の前処理条件としては、Ａ５０５２以外の各基材については、水酸化ナトリウムが５０ｇ／Ｌのアルカリ脱脂浴にてカソード電解脱脂を５Ａ／ｄｍ2で６０秒実施後、１０％硫酸およびフッ化アンモニウム５０ｇ／Ｌの酸洗溶液にて３０秒酸洗浄し、各めっき工程へ移行した。 As a pretreatment condition before each plating, for each substrate other than A5052, after performing cathode electrolytic degreasing at 5 A / dm 2 for 60 seconds in an alkaline degreasing bath containing 50 g / L of sodium hydroxide, 10%. It was pickled with a pickling solution of sulfuric acid and ammonium fluoride 50 g / L for 30 seconds, and the process proceeded to each plating step.

またＡ５０５２においては、前記のアルカリ脱脂浴にてカソード電解脱脂を５Ａ／ｄｍ2で１０秒実施後、１０％硫酸およびフッ化アンモニウム５０ｇ／Ｌの酸洗溶液にて１０秒酸洗浄した後、水酸化ナトリウムを５０ｇ／Ｌ、酸化亜鉛を５ｇ／Ｌ、塩化第二鉄を２ｇ／Ｌ、ロッシェル塩を５０ｇ／Ｌをそれぞれ含有した亜鉛置換浴で、浴温２５℃、処理時間１０秒処理して亜鉛置換を実施し、もう一度前記の酸洗浄と亜鉛置換を繰り返して各めっき工程へ移行した。 In A5052, cathode electrolytic degreasing was carried out at 5 A / dm 2 for 10 seconds in the alkaline degreasing bath, then pickled with a pickling solution of 10% sulfuric acid and 50 g / L of ammonium fluoride for 10 seconds, and then water. In a zinc replacement bath containing 50 g / L of sodium oxide, 5 g / L of zinc oxide, 2 g / L of ferric chloride, and 50 g / L of Rochelle salt, the bath temperature was 25 ° C. and the treatment time was 10 seconds. Zinc substitution was carried out, and the above-mentioned pickling and zinc substitution were repeated once again to move to each plating step.

各めっき処理は、電気めっきにて、めっき浴の組成、めっき液の温度、電流密度及びめっき時間を調製することで行った。表２に実施例１～５でそれぞれ用いた電気めっき条件を示す。めっき浴成分は、Ｎｉメタル分１３０ｇ／Ｌ、ホウ酸２５ｇ／ＬでｐＨ３．３であった。ここで、Ｎｉメタル分は、Ｎｉ塩としてスルファミン酸ニッケル四水和物及び塩化Ｎｉで構成されている。より具体的には、スルファミン酸ニッケル四水和物：Ｎｉ（ＮＨ2ＳＯ3）2・４Ｈ2Ｏ＝２９４ｇ／Ｌ（約３００ｇ／Ｌ）、Ｎｉ量で５３．５ｇ／Ｌ、塩化ニッケル六水和物：ＮｉＣｌ2・６Ｈ2Ｏ＝約３１０ｇ／Ｌ、Ｎｉ量で７６．５ｇ／Ｌである。 Each plating treatment was performed by electroplating by adjusting the composition of the plating bath, the temperature of the plating solution, the current density and the plating time. Table 2 shows the electroplating conditions used in Examples 1 to 5, respectively. The plating bath components had a Ni metal content of 130 g / L, boric acid of 25 g / L, and a pH of 3.3. Here, the Ni metal component is composed of nickel sulfamate tetrahydrate and Ni chloride as Ni salts. More specifically, nickel sulfamate tetrahydrate: Ni (NH 2 SO 3 ) 2.4H 2 O = 294 g / L (about 300 g / L), Ni amount 53.5 g / L, nickel chloride hexahydrate Japanese product: NiCl 2.6H 2 O = about 310 g / L, and the amount of Ni is 76.5 g / L.

実施例６～１４及び１７～２０、従来例１、比較例１～２の表層めっき、及び、実施例１５～１６の下地めっき及び表層めっきは、上記実施例１～５の表２で用いためっき条件に基づき、めっき浴の組成、めっき液の温度、電流密度及びめっき時間、さらに撹拌の程度をそれぞれ調整することで形成した。このとき、導電性材料の試験片の表面のＳａ、Ｓｐｄ、Ｓｚが所望の数値となるように、上記実施例１～５の表２で用いためっき条件と後述の評価結果を参考にした。また、各めっき条件の調整は以下の知見に基づいて行った。
膜厚：膜厚が増加すると、結晶粒が膜厚方向に優先的に成長する（水平方向よりも膜厚方向への成長速度が速い）ため、Ｓａ、Ｓｚは大きくなる。一方、Ｓｐｄについては、隣り合った結晶が合体しやすくなるため、極大値を５μｍ位でとり、それ以上の膜厚は低下する傾向にある。
めっき液種類：めっき液中の塩素濃度、すなわち塩化Ｎｉ濃度を大きくすることで、結晶が尖りやすく、また表面の凹凸が大きくなるため、Ｓａ、Ｓｚ、Ｓｐｄがそれぞれ増大する。
めっき液温度：めっき浴の液温が高いと、結晶が等方的に成長し、結晶粒が大きくなりやすいため、Ｓａ、Ｓｚ、Ｓｐｄはそれぞれ増加する。一方で、６０℃を超えると結晶粒粗大化が進行し、極大値を５５℃近辺でとってやがて低下する。
電流密度：電流密度が高くなると、核生成数が多くなるため、膜厚が薄い場合と厚い場合に分けて考えられる。概ね３μｍ前後で差があり、３μｍ以下であれば電流密度が高いとＳａ、Ｓｚは微細析出が優先となり小さくなる傾向にある、Ｓｐｄは各発生数が増えて突起の数が多くなるため大きくなる傾向にある。一方で、膜厚が厚いとＳａ、Ｓｚは上記膜厚上昇と同じ要因で増加し、他方で隣り合った結晶が合体してＳｐｄが低下する傾向にある。
なお、従来例２は、特許文献３の実施例に基づき、以下の条件で導電性材料の試験片を作製した。具体的には、従来例２のＮｉめっきは、硫酸ニッケルを２６０ｇ／Ｌ、塩化ニッケルを５０ｇ／Ｌ、ホウ酸を３５ｇ／Ｌ、ｐＨ４．５、浴温５０℃、電流密度５Ａ／ｄｍ2、めっき時間２００秒の条件で作製した。
さらに実施例１５、１６および従来例２に記載のＡｕめっきについては、シアン化金カリウムを２０ｇ／Ｌ、クエン酸カリウムを５０ｇ／Ｌ、ｐＨ５、浴温６０℃、電流密度１Ａ／ｄｍ2で所定の膜厚になるようにめっき時間を調整し、またＰｄめっきにおいては、ジアンミンジクロロパラジウムをＰｄ成分として２０ｇ／Ｌ、塩化アンモニウムを７５ｇ／Ｌ、ｐＨ９、浴温４０℃、電流密度１．５Ａ／ｄｍ2で所定の膜厚になるようにめっき時間を調整して作製した。従来例２のめっき厚は１μｍとした。
なお、めっき厚の確認については、任意の５点について蛍光Ｘ線膜厚計（日立ハイテク社製 ＳＦＴ９５００）を使用し、コリメータ径０．２ｍｍ、各膜厚測定時間３０秒での平均値について算出した。 The surface plating of Examples 6 to 14 and 17 to 20, Conventional Example 1 and Comparative Examples 1 to 2, and the base plating and surface plating of Examples 15 to 16 were used in Table 2 of Examples 1 to 5. It was formed by adjusting the composition of the plating bath, the temperature of the plating solution, the current density and the plating time, and the degree of stirring based on the plating conditions. At this time, the plating conditions used in Table 2 of Examples 1 to 5 and the evaluation results described later were referred to so that Sa, Spd, and Sz on the surface of the test piece of the conductive material had desired values. In addition, the adjustment of each plating condition was performed based on the following findings.
Film thickness: As the film thickness increases, the crystal grains grow preferentially in the film thickness direction (the growth rate in the film thickness direction is faster than in the horizontal direction), so that Sa and Sz increase. On the other hand, with respect to Spd, since adjacent crystals are likely to coalesce, a maximum value of about 5 μm is taken, and the film thickness beyond that tends to decrease.
Plating solution type: By increasing the chlorine concentration in the plating solution, that is, the Ni chloride concentration, the crystals tend to be sharpened and the surface irregularities become large, so that Sa, Sz, and Spd increase, respectively.
Plating liquid temperature: When the liquid temperature of the plating bath is high, the crystals grow isotropically and the crystal grains tend to become large, so that Sa, Sz, and Spd increase respectively. On the other hand, when the temperature exceeds 60 ° C, grain grain coarsening progresses, and the maximum value is eventually lowered at around 55 ° C.
Current density: As the current density increases, the number of nucleations increases, so it is possible to consider the case where the film thickness is thin and the case where the film thickness is thick. There is a difference at about 3 μm, and if the current density is 3 μm or less, Sa and Sz tend to be smaller due to the priority of fine precipitation, and Spd becomes larger because the number of each generation increases and the number of protrusions increases. There is a tendency. On the other hand, when the film thickness is thick, Sa and Sz tend to increase due to the same factor as the above-mentioned film thickness increase, and on the other hand, adjacent crystals tend to coalesce and Spd decreases.
In Conventional Example 2, a test piece of a conductive material was produced under the following conditions based on the examples of Patent Document 3. Specifically, in the Ni plating of Conventional Example 2, nickel sulfate is 260 g / L, nickel chloride is 50 g / L, boric acid is 35 g / L, pH 4.5, bath temperature is 50 ° C., and current density is 5 A / dm 2 . It was manufactured under the condition that the plating time was 200 seconds.
Further, for Au plating described in Examples 15 and 16 and Conventional Example 2, predetermined gold potassium cyanide is 20 g / L, potassium citrate is 50 g / L, pH 5, bath temperature is 60 ° C., and current density is 1 A / dm 2 . In Pd plating, 20 g / L of diamminedichloropalladium as a Pd component, 75 g / L of ammonium chloride, pH 9, bath temperature 40 ° C., current density 1.5 A / It was produced by adjusting the plating time so as to have a predetermined film thickness at dm 2 . The plating thickness of Conventional Example 2 was 1 μm.
To check the plating thickness, use a fluorescent X-ray film thickness meter (SFT9500 manufactured by Hitachi High-Tech) for any 5 points, and calculate the average value at a collimator diameter of 0.2 mm and each film thickness measurement time of 30 seconds. did.

実施例２１については、実施例１と同じ条件で６μｍのＮｉめっきを行った後、Ｎｉめっき厚を５μｍとなるまで以下の条件にてエッチングした。
・エッチング条件
エッチング液：メック社製ＮＲ１８７０、エッチング液温：２５℃、エッチング時間：３０秒 For Example 21, 6 μm of Ni plating was performed under the same conditions as in Example 1, and then etching was performed under the following conditions until the Ni plating thickness became 5 μm.
・ Etching conditions Etching liquid: NR1870 manufactured by MEC, etching liquid temperature: 25 ° C, etching time: 30 seconds

＜評価＞
・表面のＳａ、Ｓｐｄ、Ｓｚ
導電性材料の試験片の表面のＳａ、Ｓｐｄ、Ｓｚは、キーエンス社製レーザー顕微鏡（ＶＫ－Ｘ１５０）を使用し、観察倍率１０００倍、スポット径φ０．８ｍｍ、測定面積１００μｍ×１００μｍで測定した。５回の測定（Ｎ５）の平均値を算出し、導電性材料の試験片の表面のＳａ、Ｓｐｄ、Ｓｚの値とした。 <Evaluation>
-Sa, Spd, Sz on the surface
The Sa, Spd, and Sz on the surface of the test piece of the conductive material were measured using a laser microscope (VK-X150) manufactured by KEYENCE Corporation with an observation magnification of 1000 times, a spot diameter of φ0.8 mm, and a measurement area of 100 μm × 100 μm. The average value of the five measurements (N5) was calculated and used as the Sa, Spd, and Sz values on the surface of the test piece of the conductive material.

・シェア強度（初期）
導電性材料の試験片の表面に樹脂成型したものをサンプルとして、プリンカップモールド試験にてシェア強度を測定した。試験条件は、樹脂：日立化成社製ＧＥ－７４７０ＬＡ樹脂、プリンカップ底面の面積：１０ｍｍ2、樹脂成型時間：１２０秒、モールドキュア：１７５℃で８時間とし、１０回のせん断力測定（Ｎ１０）の平均値を算出し、シェア強度（初期）とした。シェアはデイジ社製 ボンドテスター（Ｓｅｒｉｅｓ４０００）にて、シェア速度１００μｍ／秒にて測定した。評価基準は以下の通りとした。
◎：２０ｋｇ以上
〇：１５ｋｇ以上２０ｋｇ未満
×：１５ｋｇ未満 ・ Share strength (initial)
The shear strength was measured by a pudding cup mold test using a resin-molded sample on the surface of a test piece of a conductive material as a sample. The test conditions were resin: GE-7470LA resin manufactured by Hitachi Kasei Co., Ltd., area of the bottom of the pudding cup: 10 mm 2 , resin molding time: 120 seconds, mold cure: 175 ° C. for 8 hours, and 10 shear force measurements (N10). The average value of was calculated and used as the share strength (initial). The share was measured with a bond tester (Series 4000) manufactured by Daige Co., Ltd. at a share speed of 100 μm / sec. The evaluation criteria are as follows.
◎: 20 kg or more 〇: 15 kg or more and less than 20 kg ×: less than 15 kg

・シェア強度（高温高湿試験）
また、上記のように作製したサンプルを、温度８５℃、湿度８５％の環境下で１６８時間放置した後、上記シェア強度を同様に測定した。評価基準は以下の通りとした。
◎：剥離無し
〇：剥離率２０％未満
×：剥離率２０％以上
当該剥離率は、超音波探傷による画像から、導電性材料の表面と樹脂とがどのような割合で剥離しているのかを計算して評価した。 ・ Share strength (high temperature and high humidity test)
Further, the sample prepared as described above was left to stand in an environment of a temperature of 85 ° C. and a humidity of 85% for 168 hours, and then the share strength was measured in the same manner. The evaluation criteria are as follows.
◎: No peeling 〇: Peeling rate less than 20% ×: Peeling rate 20% or more The peeling rate is the ratio of the surface of the conductive material and the resin peeling from the image obtained by ultrasonic flaw detection. Calculated and evaluated.

・シェア強度（ヒートサイクル試験）
さらに、上記のように作製したサンプルを、１２５℃で３０分間保持した後、－４０℃で３０分間保持することを１サイクルとして、これを５００サイクル連続で繰り返した。その後、上記シェア強度を同様に測定した。評価基準は以下の通りとした。
◎：剥離無し
〇：剥離率１０％未満
△：剥離率１０％以上２０％未満
×：剥離率２０％以上
当該剥離率は、超音波探傷による画像から、導電性材料の表面と樹脂とがどのような割合で剥離しているのかを計算して評価した。
上記試験条件及び評価結果を表１、２に示す。 ・ Share strength (heat cycle test)
Further, the sample prepared as described above was held at 125 ° C. for 30 minutes and then held at −40 ° C. for 30 minutes as one cycle, and this was repeated for 500 consecutive cycles. Then, the share strength was measured in the same manner. The evaluation criteria are as follows.
⊚: No peeling 〇: Peeling rate less than 10% △: Peeling rate 10% or more and less than 20% ×: Peeling rate 20% or more From the image obtained by ultrasonic flaw detection, which is the surface of the conductive material and the resin? It was calculated and evaluated whether it was peeled off at such a rate.
The above test conditions and evaluation results are shown in Tables 1 and 2.

Figure 0007014695000001
Figure 0007014695000001

Figure 0007014695000002
Figure 0007014695000002

実施例１～２１は、いずれも導電性材料の表面が下記（１）及び（２）の条件を満たしたため、初期、高温高湿試験のいずれのシェア強度も非常に良好であり、ヒートサイクル試験のシェア強度は評価基準が△、〇、◎のいずれかであり、過酷な環境下においても優れた樹脂密着性を示すことがわかった。
（１）算術平均面粗さ高さＳａが０．２５～０．４μｍ、
（２）山の頂点密度Ｓｐｄが１ｍｍ2あたり２５０万個以上
従来例１、２及び比較例１、２は、いずれも導電性材料の表面が上記（１）及び（２）の条件の少なくとも１つを満たさなかったため、少なくともヒートサイクル試験のシェア強度が不良であった。 In Examples 1 to 21, since the surface of the conductive material satisfied the following conditions (1) and (2), the share strengths of both the initial and high temperature and high humidity tests were very good, and the heat cycle test was performed. It was found that the share strength of No. 1 had an evaluation standard of △, 〇, or ◎, and showed excellent resin adhesion even in a harsh environment.
(1) Arithmetic mean surface roughness height Sa is 0.25 to 0.4 μm,
(2) The peak density Spd of the mountain is 2.5 million or more per 1 mm 2. In both Conventional Examples 1 and 2 and Comparative Examples 1 and 2, the surface of the conductive material is at least one of the conditions (1) and (2) above. At least the share strength of the heat cycle test was poor because it did not meet the above requirements.

１０、２０、３０ 導電性材料
１１、２１、３１ 表面
１２、２４、３５ 点線枠
２２、３２ 基材
２３ めっき層
３３ 第１めっき層
３４ 第２めっき層 10, 20, 30 Conductive material 11, 21, 31 Surface 12, 24, 35 Dotted line frame 22, 32 Base material 23 Plating layer 33 First plating layer 34 Second plating layer

Claims (11)

表面に樹脂を成型する、または、表面を樹脂で封止する導電性材料であって、
前記表面が金属で構成され、下記（１）及び（２）の条件を満たす導電性材料。
（１）算術平均面粗さ高さＳａが０．２５～０．４μｍ、
（２）山の頂点密度Ｓｐｄが１ｍｍ2あたり２５０万個以上。 A conductive material that forms a resin on the surface or seals the surface with a resin.
A conductive material whose surface is made of metal and which satisfies the following conditions (1) and (2).
(1) Arithmetic mean surface roughness height Sa is 0.25 to 0.4 μm,
(2) The peak density Spd of the mountain is 2.5 million or more per 1 mm 2 . 前記表面の最大面粗さ高さＳｚが３．５～６．５μｍである請求項１に記載の導電性材料。 The conductive material according to claim 1, wherein the maximum surface roughness height Sz of the surface is 3.5 to 6.5 μm. 前記導電性材料が基材と前記基材上に形成されためっき層とを含み、
前記表面が前記めっき層である請求項１または２に記載の導電性材料。 The conductive material comprises a substrate and a plating layer formed on the substrate.
The conductive material according to claim 1 or 2, wherein the surface is the plating layer. 前記基材が、銅、銅合金、アルミニウム、アルミニウム合金、鉄及び鉄合金のいずれかで構成された請求項３に記載の導電性材料。 The conductive material according to claim 3, wherein the base material is made of any one of copper, a copper alloy, aluminum, an aluminum alloy, iron and an iron alloy. 前記めっき層が１種以上のめっき層で構成された請求項３または４に記載の導電性材料。 The conductive material according to claim 3 or 4, wherein the plating layer is composed of one or more types of plating layers. 前記めっき層は前記基材上に形成された第１めっき層を有し、前記第１めっき層が銅、銅合金、ニッケル及びニッケル合金のいずれかで構成された請求項５に記載の導電性材料。 The conductivity according to claim 5, wherein the plating layer has a first plating layer formed on the substrate, and the first plating layer is made of any one of copper, a copper alloy, nickel and a nickel alloy. material. 前記めっき層は前記第１めっき層上に形成された第２めっき層を有し、前記第２めっき層がパラジウム、パラジウム合金、金及び金合金のいずれかで構成された請求項６に記載の導電性材料。 The sixth aspect of claim 6, wherein the plating layer has a second plating layer formed on the first plating layer, and the second plating layer is made of any of palladium, a palladium alloy, gold, and a gold alloy. Conductive material. 前記１種以上のめっき層で構成された前記めっき層の厚みの総和が１～７μｍである請求項５～７のいずれか一項に記載の導電性材料。 The conductive material according to any one of claims 5 to 7, wherein the total thickness of the plating layers composed of the one or more types of plating layers is 1 to 7 μm. 前記（１）及び（２）の条件を満たす表面を部分的に有する請求項１～８のいずれか一項に記載の導電性材料。 The conductive material according to any one of claims 1 to 8, which partially has a surface satisfying the conditions of (1) and (2). 前記表面に樹脂が成型された、または、前記表面が樹脂で封止された請求項１～９のいずれか一項に記載の導電性材料を備えた成型品。 The molded product provided with the conductive material according to any one of claims 1 to 9, wherein a resin is molded on the surface or the surface is sealed with the resin. 請求項１～９のいずれか一項に記載の導電性材料を備えた電子部品。 An electronic component comprising the conductive material according to any one of claims 1 to 9.
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