WO2015012306A1 - Electronic component and process for producing same - Google Patents

Electronic component and process for producing same Download PDF

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Publication number
WO2015012306A1
WO2015012306A1 PCT/JP2014/069435 JP2014069435W WO2015012306A1 WO 2015012306 A1 WO2015012306 A1 WO 2015012306A1 JP 2014069435 W JP2014069435 W JP 2014069435W WO 2015012306 A1 WO2015012306 A1 WO 2015012306A1
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WIPO (PCT)
Prior art keywords
alloy
electronic component
plating film
copper
compound
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PCT/JP2014/069435
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French (fr)
Japanese (ja)
Inventor
伊森　徹
大内　高志
累 難波
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Jx日鉱日石金属株式会社
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Priority to JP2015528305A priority Critical patent/JP6192181B2/en
Priority to KR1020157020118A priority patent/KR101688756B1/en
Publication of WO2015012306A1 publication Critical patent/WO2015012306A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/04—Electrophoretic coating characterised by the process with organic material
    • 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
    • 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
    • C25D5/623—Porosity of the 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 an electronic component such as a connector, which is a connection component for an electronic device, and a manufacturing method thereof.
  • a material obtained by applying nickel base plating to brass or phosphor bronze and further applying gold plating thereon is generally used for a connector which is a connection part for an electronic device.
  • gold since gold is expensive, various methods have been adopted for the purpose of reducing the connector manufacturing cost.
  • a typical method is a method of reducing the thickness of the gold plating.
  • the pinholes of the film increase exponentially and the corrosion resistance is remarkably reduced.
  • One method for solving this problem is sealing. That is, the surface of the gold plating is treated with various inorganic or organic chemicals to close the pinholes and improve the corrosion resistance.
  • sealing treatment liquids organic and aqueous.
  • Patent Documents 1 to 3 describe the sealing agents used, and Patent Documents 4 to 5 describe sealing agents having specific triazine compounds as inhibitors.
  • Phosphor bronze base materials tend to be used for switches and connector parts, and beryllium copper is used for battery terminal connectors and the like that are more required to have springiness and wear resistance.
  • Beryllium copper is a ductile metal material that can be welded and machined. It is also a material that can withstand non-oxidizing acids (hydrochloric acid, carbonic acid, etc.), substances that break down plastics, abrasive wear and scuffing. Furthermore, if heat treatment is applied, strength, durability, and electrical conductivity can be increased. Beryllium copper boasts the highest strength (up to 1400 MPa) among copper-based alloys. However, since beryllium compounds are toxic, there are safety concerns regarding beryllium copper alloys.
  • beryllium copper has no particular health impact, but inhalation of beryllium copper dust from machining and welding processes can cause serious lung effects.
  • beryllium compounds are recommended by IARC as having carcinogenicity (Type 1).
  • IARC carcinogenicity
  • nickel bronze Cu—Ni—Sn
  • titanium copper may be used as an alternative to beryllium copper.
  • nickel bronze has a problem of poor yield.
  • Titanium copper is a special copper alloy containing Ti as a main accessory component. In terms of strength, stress relaxation resistance and bending workability, it has properties comparable to beryllium copper alloys, which are representative of high strength and high performance copper alloys. For this reason, the use of titanium copper in place of beryllium copper alloy has been greatly increasing in recent years mainly for use in base materials such as connector terminals, battery terminals, burn-in sockets, etc. in electronic devices such as personal computers and mobile phones.
  • the Corson alloy is a kind of special copper alloy containing Ni and Si as main subcomponents. Because of its high strength and high electrical conductivity and excellent bending workability, it is mainly used for connector terminals and lead frames of electronic devices such as personal computers and mobile phones.
  • titanium copper or Corson alloy is used as the base material of the connector which is a connecting part for electronic equipment, and the phosphor bronze is used as the base material, nickel base plating is applied, and further gold plating is applied thereon.
  • Titanium copper has titanium oxide
  • Corson alloy has Si oxide on the surface of the copper base, so the adhesion of nickel base plating is poor, and the corrosion resistance of the plating is worse than when phosphor bronze is used.
  • the sealing treatment is performed, many pinholes are generated due to the oxidized points of the material to be plated, and the gold plating film or sealing agent formed thereon can completely block the pinholes. Inability to cause corrosion and discoloration.
  • Patent Document 6 discloses an electrical contact having a three-layer structure in which a gold-nickel alloy layer and a gold layer are sequentially laminated.
  • An electrical contact having a three-layer structure in which a nickel layer, a Pd-nickel alloy layer, and a gold layer are sequentially laminated on a copper alloy is already known. However, these techniques do not describe sealing treatment.
  • Patent Documents 7 to 8 disclose that a copper base material is sealed with a sealing agent containing a chelate-forming cyclic nitrogen compound on a material plated with Ni, Pd or Pd alloy, or Au or Au alloy. A hole treatment is disclosed.
  • the sealing agent is an organic solvent solution, and the treatment method includes impregnation treatment and coating.
  • phosphor bronze is used as a copper base material in Examples.
  • the impregnation treatment using the sealing treatment agent and the sealing treatment by coating did not provide a corrosion resistance effect. .
  • Japanese Patent No. 2804442 Japanese Patent No. 2717062 JP 2003-129257 A JP-A-5-31490 JP-A-5-311491 JP 2002-231357 A JP-A-4-193882 Japanese Patent Laid-Open No. 4-193990
  • the present invention uses titanium copper or a Corson alloy as a base material, and in an electronic component having an Au or Au alloy plating film, even if the Au or Au alloy plating film is thin, the occurrence of pinholes is small.
  • An object of the present invention is to provide an electronic component that is resistant to corrosion and discoloration and has excellent corrosion resistance, and a method for manufacturing the same.
  • the present invention is as follows.
  • an electronic component using titanium copper or a Corson alloy as a substrate and having an Au or Au alloy plating film even if the Au or Au alloy plating film is thin, the occurrence of pinholes is small, and corrosion or discoloration of titanium copper is caused. Can be provided, and an electronic component having excellent corrosion resistance and a method for manufacturing the same can be provided.
  • the electronic component of the present invention has three layers of a Ni plating film, a Pd—Ni plating film, and an Au or Au alloy plating film on a substrate made of titanium copper or a Corson alloy, and further the surface of the Au or Au alloy plating film.
  • an electrodeposition treatment is performed using a sealing agent containing a benzotriazole compound, a mercaptobenzothiazole compound, or a triazine thiol compound as an inhibitor.
  • titanium copper or a Corson alloy is used as a base material. Titanium copper is a special copper alloy obtained by adding 1.0 to 4.0% by mass of titanium to copper, and may further contain iron or the like.
  • Titanium copper has properties comparable to beryllium copper alloys, which are typical of high strength and high function copper alloys, in strength, stress relaxation resistance and bending workability.
  • the Corson alloy is a kind of special copper alloy mainly composed of copper and mainly composed of Ni and Si, and may further contain magnesium, tin, zinc, cobalt, chromium, manganese and the like. Corson alloy has high strength and electrical conductivity, and is excellent in bending workability.
  • the Ni plating film and the Pd—Ni plating film By forming the Ni plating film and the Pd—Ni plating film on the base material, pinholes existing in the Pd—Ni film can be reduced, and the base material can be prevented from being exposed. Further, the thickness of the Au or Au alloy plating film can be reduced.
  • the surface of the Au or Au alloy plating film is electrodeposited using a sealing agent containing a benzotriazole compound, a mercaptobenzothiazole compound, or a triazine thiol compound as an inhibitor. It is important to be made. By performing electrodeposition using a sealing agent containing a specific inhibitor, pinholes can be further reduced, and corrosion and discoloration of the substrate can be more reliably prevented. When the sealing treatment is not performed or when the sealing treatment is not an electrodeposition treatment, the effect of reducing pinholes is not sufficient, and the substrate is corroded and discolored.
  • a sealing treatment using an inhibitor other than the benzotriazole-based compound, mercaptobenzothiazole-based compound, or triazine thiol-based compound, or a treatment using the inhibitor reflow is performed.
  • the treatment is performed, the effect of the sealing treatment is lost.
  • the electrodeposition treatment using the sealing agent makes it possible to further process the inside of the pinhole. Therefore, even if the reflow treatment is performed, the effect of the sealing treatment is not lost.
  • the effect of the sealing process is maintained even when the maximum temperature is heated to 240 ° C. or higher. In the present invention, it is confirmed that there is an effect of sealing treatment up to 280 ° C.
  • the method for manufacturing an electronic component according to the present invention includes forming three layers of a Ni plating film, a Pd—Ni plating film, Au or an Au alloy plating film in this order on a substrate made of titanium copper or a Corson alloy, and Au or Au alloy.
  • the plating film surface is subjected to electrodeposition treatment using a sealing agent containing a benzotriazole compound, mercaptobenzothiazole compound, or triazine thiol compound as an inhibitor.
  • titanium copper has characteristics comparable to beryllium copper alloys, which are typical of high-strength and high-function copper alloys, in strength, stress relaxation resistance, and bending workability.
  • the electronic component of the present invention using titanium copper as a base material can be suitably used mainly for applications such as connector terminals, battery terminals, and burn-in sockets of electronic devices such as personal computers and mobile phones.
  • the Ni plating film is preferably formed by electrolytic plating.
  • the electrolytic Ni plating solution a known plating solution used for manufacturing electronic components can be used.
  • a Ni plating solution such as a sulfamic acid bath or a watt bath can be preferably used.
  • Ni plating conditions may also be known plating conditions.
  • the thickness of the Ni plating film is preferably 0.5 to 5 ⁇ m.
  • the Pd—Ni plating film is preferably formed by electrolytic plating.
  • the electrolytic Pd—Ni plating solution a known plating solution used for manufacturing electronic components can be used.
  • a Pd—Ni plating solution such as an ammonia bath can be preferably used.
  • the Pd—Ni plating film preferably contains 5 to 50% by mass of Ni.
  • the Pd—Ni plating conditions may also be known plating conditions.
  • the thickness of the Pd—Ni plating film is preferably 0.05 to 1 ⁇ m.
  • the Au or Au alloy plating film is preferably formed by electrolytic plating.
  • the electrolytic Au plating solution and the Au alloy plating solution a known plating solution used for manufacturing electronic components can be used. Weakly acidic type Au plating solution and Au—Co alloy (Co 0.2 to 0.5 mass%) plating are preferable.
  • a citric acid bath plating solution can be preferably used.
  • the conditions for Au plating and Au alloy plating may be known plating conditions.
  • the thickness of the Au or Au alloy plating film is preferably 0.01 to 0.1 ⁇ m.
  • the electronic component of the present invention is obtained by performing an electrodeposition treatment using a sealing agent on an Au plating film.
  • a sealing agent a sealing agent containing a benzotriazole compound, a mercaptobenzothiazole compound, or a triazine thiol compound as an inhibitor is used.
  • the benzotriazole-based compound has the following general formula (1) (Wherein R 1 represents hydrogen, alkyl, or substituted alkyl, and R 2 represents an alkali metal, hydrogen, alkyl, or substituted alkyl) It is represented by Preferred examples of the compound represented by the general formula (1) include 1H benzotriazole (both R 1 and R 2 are hydrogen), 1-methylbenzotriazole (R 1 is hydrogen, R 2 is methyl), Tolyltriazole (R 1 is methyl, R 2 is hydrogen), 1- (N, N-dioctylaminomethyl) benzotriazole (R 1 is hydrogen, R 2 is N, N-dioctylaminomethyl) and the like.
  • R 1 represents hydrogen, alkyl, or substituted alkyl
  • R 2 represents an alkali metal, hydrogen, alkyl, or substituted alkyl
  • Preferred examples of the compound represented by the general formula (1) include 1H benzotriazole (both R 1 and R 2 are hydrogen), 1-methylbenzo
  • the mercaptobenzothiazole compound has the general formula (2) (Wherein R 3 represents an alkali metal or hydrogen) It is represented by Preferred examples of the compound represented by the general formula (2) include 2-mercaptobenzothiazole, sodium salt of 2-mercaptobenzothiazole, and potassium salt of 2-mercaptobenzothiazole.
  • R 3 represents an alkali metal
  • the mercaptobenzothiazole compound is easily dissolved in water.
  • Triazine thiol compounds are represented by the general formula (3) [Wherein R 4 is —SH, an amino group substituted with an alkyl group or an aryl group, or an alkyl-substituted imidazolylalkyl, R 5 , R 6 are —NH 2 , —SH or —SM (M represents an alkali metal) ). However, at least one of R 4 , R 5 and R 6 is —SH or —SM. ] It is represented by Preferred examples of the compound represented by the general formula (3) include the following.
  • alkali metal salts such as Na or K.
  • R 5 and R 6 are —SM, the triazine thiol compound can be easily dissolved in water.
  • the addition amount of the inhibitor is in the range of 0.001 to 1 wt%. If it is less than 0.001 wt%, the sealing treatment effect is not observed, and if it exceeds 1 wt%, an adverse effect on the contact resistance is recognized.
  • the processing agent used for the sealing treatment of the present invention may further contain a lubricant.
  • the lubricant is preferably a fatty acid, and contributes to improving the lubricity of the gold plating material by adding to the sealing agent.
  • the fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid.
  • the amount of lubricant added is preferably in the range of 0.05 wt% to 2 wt%. If it is less than 0.05 wt%, it is difficult to obtain a lubricating effect, and if it exceeds 2 wt%, an adverse effect on the appearance of the material after the sealing treatment is observed.
  • the processing agent used for the sealing treatment of the present invention may contain an emulsifier, and the emulsifier is preferably a monoalkyl phosphate ester or a dialkyl phosphate ester.
  • the emulsifier is added to the treating agent and functions as an emulsifier for the lubricant. Furthermore, the emulsifier also has a lubricating action.
  • the monoalkyl phosphate ester and dialkyl phosphate ester are obtained by dehydration condensation of phosphoric acid and an aliphatic alcohol. Examples of the aliphatic alcohol include decyl alcohol, lauryl alcohol, myristyl alcohol, cetanol, and stearyl alcohol. preferable.
  • These may be monoesters or diesters, and each may be used alone, but a mixture of monoesters and diesters or a mixture of a plurality of phosphate esters having different alcohol components may be used. Absent. As these monoalkyl phosphate esters and dialkyl phosphate esters, commercially available products can be used.
  • the added amount of the emulsifier is in the range of 0.05 wt% to 2 wt%. If it is less than 0.05 wt%, the emulsifying effect is difficult to obtain, and if it exceeds 2 wt%, an adverse effect on solderability is observed.
  • the sealing treatment liquid is an aqueous solution having the above components, and the temperature of the solution is preferably 10 to 80 ° C., more preferably 30 to 50 ° C. By setting the temperature to 10 to 80 ° C., the emulsification of the components in water proceeds more rapidly, and the material after the sealing treatment can be easily dried.
  • a treatment method a plated product is immersed in a treatment solution, and a direct current or a pulse current is passed between the electrodes using the material as an anode. By using the plated product as an anode, the inhibitor in the solution is adsorbed to the base metal inside the pinhole of the plated product and prevents its corrosion.
  • the current density is preferably 0.1 mA / dm 2 or more, more preferably 1 to 100 mA / dm 2 . If it is less than 0.1 mA / dm 2 , the sealing treatment effect cannot be obtained.
  • the processing time is preferably 1 to 10 seconds.
  • the product of the current density and the processing time is preferably 10 to 1000 mA ⁇ sec / dm 2 , more preferably 20 to 200 mA ⁇ sec / dm 2 .
  • the electronic component of the present invention includes a connector that is a connecting component for electronic equipment.
  • a connector that is a connecting component for electronic equipment.
  • it can be suitably used for a battery terminal connector that requires more springiness and wear resistance.
  • the plated substrate based on titanium copper was subjected to sealing treatment by electrodeposition under the conditions of Examples 1 to 4 or Comparative Example 3 in Table 1, sufficiently washed with water, and then dried with a drier to seal the plating. An agent film was formed. Further, a sealing treatment film was formed on the plated substrate based on the Corson alloy by the same electrodeposition under the conditions of Example 5.
  • sealing treatment was not performed on a plated substrate based on titanium copper.
  • sealing treatment was performed by dipping treatment on a plated substrate based on titanium copper.
  • ion-exchange water was used for the solvent of the sealing agent.
  • the lauryl phosphate ester and decyl phosphate ester used for the sealing agent are a mixture of a monoester and a diester.
  • the obtained substrate was subjected to reflow treatment (atmospheric atmosphere) with the profile shown in FIG. 1 and then subjected to a salt spray test (based on JISZ2371) for 72 hours to evaluate corrosion resistance.
  • the results are shown in Table 1. Evaluation criteria: ⁇ : Almost no corrosion. ⁇ : Black spot-like corrosion is observed in some places. X: A brown and / or green corrosion point is observed in some places.
  • the comparative example 3 is an example using the sealing agent different from the sealing agent concerning this invention.
  • the sealing agent used in Comparative Example 3 has been confirmed to have an effect of corrosion resistance when phosphor bronze (C5210, 25 mm ⁇ 20 mm ⁇ 0.2 mmt) is used as a base material. That is, Comparative Example 3 shows that a sealing agent effective for a phosphor bronze base material is not effective for sealing a titanium copper base material as it is.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The purpose of the present invention is to provide: an electronic component which includes a base comprising titanium-copper or Corson ally and an Au or Au-alloy coating film formed by plating, wherein the Au or Au-alloy coating film has few pinholes even when thin and the titanium-copper or Corson alloy is less apt to suffer corrosion or discoloration, resulting in excellent corrosion resistance; and a process for producing the electronic component. This electronic component is characterized by comprising: a base constituted of titanium-copper or Corson alloy; and three layers successively formed thereon by plating, i.e., an Ni coating film, a Pd-Ni coating film, and an Au or Au-alloy coating film. The electronic component is further characterized in that the surface of the Au or Au-alloy coating film has undergone electrodeposition of a pore-filling agent which contains a benzotriazole compound, a mercaptobenzothiazole compound, or a triazinethiol compound as an inhibitor.

Description

電子部品およびその製造方法Electronic component and manufacturing method thereof
　本発明は電子機器用接続部品であるコネクタ等の電子部品およびその製造方法に関する。 The present invention relates to an electronic component such as a connector, which is a connection component for an electronic device, and a manufacturing method thereof.
　電子機器用接続部品であるコネクタには、黄銅やリン青銅にニッケル下地めっきを施し、さらに、その上に金めっきを施した材料が一般に使用される。しかし、金は高価であるために、コネクタ製造コストを下げる目的で様々な方法が採られている。その代表的な方法が金めっきの厚みを下げる方法であるが、金めっき厚を薄くするに伴って、皮膜のピンホールが指数関数的に増え、耐食性が著しく低下するという問題を抱えている。
　この問題を解決する方法のひとつに封孔処理がある。すなわち、各種の無機あるいは有機性の薬品で金めっき表面を処理し、ピンホールを塞ぎ、耐食性を向上させようとするものである。封孔処理液には有機系と水系の２種類がある。有機系では溶媒としてハロゲン系有機溶剤が一般に使用されているため、オゾン層破壊などの問題で現在有機系封孔処理液の使用は大きく制限されている。一方、水系では溶媒として水を使用するため環境汚染の点で問題はないが、従来の有機系封孔処理液に使用されている水に難溶性のパラフィン等の潤滑剤が使用できないため、水系で処理しためっきは潤滑性が低く、コネクタの耐久性が有機系よりも劣るという問題があった。 For a connector which is a connection part for an electronic device, a material obtained by applying nickel base plating to brass or phosphor bronze and further applying gold plating thereon is generally used. However, since gold is expensive, various methods have been adopted for the purpose of reducing the connector manufacturing cost. A typical method is a method of reducing the thickness of the gold plating. However, as the gold plating thickness is reduced, there is a problem that the pinholes of the film increase exponentially and the corrosion resistance is remarkably reduced.
One method for solving this problem is sealing. That is, the surface of the gold plating is treated with various inorganic or organic chemicals to close the pinholes and improve the corrosion resistance. There are two types of sealing treatment liquids: organic and aqueous. Since organic halogen solvents are generally used as organic solvents, the use of organic sealing liquids is currently greatly restricted due to problems such as ozone layer destruction. On the other hand, there is no problem in terms of environmental pollution because water is used as a solvent in the water system, but since a lubricant such as paraffin or the like that is hardly soluble in water used in conventional organic sealing liquids cannot be used, The plating treated with the above has a problem that the lubricity is low and the durability of the connector is inferior to that of the organic type.
　そこで、環境汚染性に問題なく、かつ、従来と同等もしくはそれ以上の封孔処理効果を有する封孔処理剤として、インヒビターとして、ベンゾトリアゾール系化合物、メルカプトベンゾチアゾール系化合物、またはトリアジンチオール系化合物を用いた封孔処理剤が特許文献１～３に、インヒビターとして特定のトリアジン系化合物を有する封孔処理剤が特許文献４～５記載されている。 Therefore, as a sealing treatment agent having no problem in environmental pollution and having a sealing treatment effect equivalent to or higher than that of the prior art, an inhibitor, a benzotriazole compound, a mercaptobenzothiazole compound, or a triazine thiol compound. Patent Documents 1 to 3 describe the sealing agents used, and Patent Documents 4 to 5 describe sealing agents having specific triazine compounds as inhibitors.
　リン青銅基材は、スイッチやコネクタ部に使用される傾向があり、ばね性や耐摩耗性がより求められるバッテリー端子用コネクタ等にはベリリウム銅が使用されている。
　ベリリウム銅には延性があり、溶接や機械加工もできる金属材料である。また、非酸化性の酸（塩酸や炭酸など）・プラスチックを分解する物質・アブレシブ摩耗やかじり傷に対しても耐える素材である。さらに、熱処理を加えれば強度や耐久性、電気伝導度を増すこともできる。ベリリウム銅は、銅をベースとした合金の中で最高の強度（～１４００ＭＰａ）を誇っている。しかし、ベリリウム化合物には毒性があるので、ベリリウム銅合金についても安全上注意すべき点がある。固体や最終製品については、ベリリウム銅が健康へ特に影響を与えることはないが、機械加工や溶接の過程で出るベリリウム銅の塵を吸い込むと、肺に深刻な影響の出る危険性がある。また、ベリリウム化合物はＩＡＲＣによって発がん性がある（Type1）と勧告されている。その結果、ニッケル青銅（Ｃｕ－Ｎｉ－Ｓｎ系）、チタン銅など、より危険性の低い銅合金がベリリウム銅の代替として用いられることもある。しかし、ニッケル青銅は歩留りが悪いという問題がある。 Phosphor bronze base materials tend to be used for switches and connector parts, and beryllium copper is used for battery terminal connectors and the like that are more required to have springiness and wear resistance.
Beryllium copper is a ductile metal material that can be welded and machined. It is also a material that can withstand non-oxidizing acids (hydrochloric acid, carbonic acid, etc.), substances that break down plastics, abrasive wear and scuffing. Furthermore, if heat treatment is applied, strength, durability, and electrical conductivity can be increased. Beryllium copper boasts the highest strength (up to 1400 MPa) among copper-based alloys. However, since beryllium compounds are toxic, there are safety concerns regarding beryllium copper alloys. For solids and finished products, beryllium copper has no particular health impact, but inhalation of beryllium copper dust from machining and welding processes can cause serious lung effects. Also, beryllium compounds are recommended by IARC as having carcinogenicity (Type 1). As a result, less dangerous copper alloys such as nickel bronze (Cu—Ni—Sn) and titanium copper may be used as an alternative to beryllium copper. However, nickel bronze has a problem of poor yield.
　チタン銅はＴｉを主な副成分とする特殊銅合金である。強度、耐応力緩和特性、曲げ加工性においては、高強度・高機能銅合金の代表格であるベリリウム銅合金に匹敵する特性を有している。このため、パソコンや携帯電話等の電子機器の主にコネクタ端子、バッテリー端子、バーンインソケット等の基材の用途でベリリウム銅合金に変えてチタン銅の使用が近年大きく伸びてきている。
　コルソン合金はＮｉ、Ｓｉを主な副成分とする特殊銅合金の１種である。強度、電気伝導度が高く、曲げ加工性に優れるためパソコンや携帯電話等の電子機器の主にコネクタ端子やリードフレーム等に使用されている。 Titanium copper is a special copper alloy containing Ti as a main accessory component. In terms of strength, stress relaxation resistance and bending workability, it has properties comparable to beryllium copper alloys, which are representative of high strength and high performance copper alloys. For this reason, the use of titanium copper in place of beryllium copper alloy has been greatly increasing in recent years mainly for use in base materials such as connector terminals, battery terminals, burn-in sockets, etc. in electronic devices such as personal computers and mobile phones.
The Corson alloy is a kind of special copper alloy containing Ni and Si as main subcomponents. Because of its high strength and high electrical conductivity and excellent bending workability, it is mainly used for connector terminals and lead frames of electronic devices such as personal computers and mobile phones.
　しかし、チタン銅やコルソン合金を電子機器用接続部品であるコネクタの基材として用い、基材としてリン青銅を用いた場合と同様に、ニッケル下地めっきを施し、さらにその上に金めっきを施すと、チタン銅はチタンの酸化物が、コルソン合金はＳｉの酸化物が銅基材表面に顔を出すため、ニッケル下地めっきの密着性が悪く、リン青銅を用いた場合よりめっき物の耐食性が悪くなる。従って、通常、これらの酸化物をエッチングして金めっきを行うが、酸化物を完全に取り除くことはできず、めっき物の耐食性が悪くなる。
　更に、封孔処理を行っても、被めっき材の酸化された点を起因にピンホールが多数発生し、その上に形成した金めっき膜や封孔処理剤ではピンホールを完全に塞ぐことができず腐食や変色の原因となっていた。 However, when titanium copper or Corson alloy is used as the base material of the connector which is a connecting part for electronic equipment, and the phosphor bronze is used as the base material, nickel base plating is applied, and further gold plating is applied thereon. Titanium copper has titanium oxide, and Corson alloy has Si oxide on the surface of the copper base, so the adhesion of nickel base plating is poor, and the corrosion resistance of the plating is worse than when phosphor bronze is used. Become. Therefore, normally, these oxides are etched and gold plating is performed, but the oxides cannot be completely removed, and the corrosion resistance of the plated product is deteriorated.
Furthermore, even if the sealing treatment is performed, many pinholes are generated due to the oxidized points of the material to be plated, and the gold plating film or sealing agent formed thereon can completely block the pinholes. Inability to cause corrosion and discoloration.
　また、前記金めっき膜の厚さを薄くした際の、皮膜のピンホールが指数関数的に増え、耐食性が著しく低下するという問題を解決するために、導電性の基材金属上に、ニッケル層、金－ニッケル合金層および金層を順次積層してなる３層構造の電気接点が特許文献６に開示されている。また、銅合金上に、ニッケル層、Ｐｄ－ニッケル合金層および金層を順次積層してなる３層構造の電気接点も既に知られている。しかし、これらの技術において、封孔処理については記載されていない。 Further, in order to solve the problem that the pinhole of the film increases exponentially when the thickness of the gold plating film is reduced and the corrosion resistance is remarkably lowered, a nickel layer is formed on the conductive base metal. Patent Document 6 discloses an electrical contact having a three-layer structure in which a gold-nickel alloy layer and a gold layer are sequentially laminated. An electrical contact having a three-layer structure in which a nickel layer, a Pd-nickel alloy layer, and a gold layer are sequentially laminated on a copper alloy is already known. However, these techniques do not describe sealing treatment.
　さらに、特許文献７～８には、銅系の基材上に、Ｎｉめっき、Ｐｄ又はＰｄ合金めっき、Ａｕ又はＡｕ合金めっきをした材料にキレート形成性環状窒素化合物を含む封孔処理剤で封孔処理することが開示されている。封孔処理剤は、有機溶媒溶液であり、処理方法としては、含浸処理、塗布等である。特許文献７～８において、実施例では銅系の基材としてリン青銅を用いている。しかし、本発明者らが検討したところ、基材として、チタン銅やコルソン銅を用いた場合、前記封孔処理剤を用いた含浸処理、塗布による封孔処理では、耐食性効果が得られなかった。 Further, Patent Documents 7 to 8 disclose that a copper base material is sealed with a sealing agent containing a chelate-forming cyclic nitrogen compound on a material plated with Ni, Pd or Pd alloy, or Au or Au alloy. A hole treatment is disclosed. The sealing agent is an organic solvent solution, and the treatment method includes impregnation treatment and coating. In Patent Documents 7 to 8, phosphor bronze is used as a copper base material in Examples. However, when the present inventors examined, when titanium copper or corson copper was used as a base material, the impregnation treatment using the sealing treatment agent and the sealing treatment by coating did not provide a corrosion resistance effect. .
特許第２８０４４５２号公報Japanese Patent No. 2804442 特許第２７１７０６２号公報Japanese Patent No. 2717062 特開２００３－１２９２５７号公報JP 2003-129257 A 特開平５－３１１４９０号公報JP-A-5-31490 特開平５－３１１４９１号公報JP-A-5-311491 特開２００２－２３１３５７号公報JP 2002-231357 A 特開平４－１９３９８２号公報JP-A-4-193882 特開平４－１９３９９０号公報Japanese Patent Laid-Open No. 4-193990
　本発明は、基材としてチタン銅やコルソン合金を用い、ＡｕまたはＡｕ合金めっき膜を有する電子部品において、ＡｕまたはＡｕ合金めっき膜が薄くてもピンホールの発生が少なく、チタン銅やコルソン合金の腐食や変色が起こりにくく、耐食性に優れた電子部品、およびその製造方法を提供することを目的とする。 The present invention uses titanium copper or a Corson alloy as a base material, and in an electronic component having an Au or Au alloy plating film, even if the Au or Au alloy plating film is thin, the occurrence of pinholes is small. An object of the present invention is to provide an electronic component that is resistant to corrosion and discoloration and has excellent corrosion resistance, and a method for manufacturing the same.
　本発明者らは、鋭意検討を行った結果、以下により前記課題が解決されることを見い出し、本発明に至った。
　即ち、本発明は以下のとおりである。
（１）チタン銅またはコルソン合金からなる基材上に、Ｎｉめっき膜、Ｐｄ－Ｎｉめっき膜、ＡｕまたはＡｕ合金めっき膜の３層を順に有し、さらにＡｕまたはＡｕ合金めっき膜表面が、インヒビターとして、ベンゾトリアゾール系化合物、メルカプトベンゾチアゾール系化合物、またはトリアジンチオール系化合物を含有する封孔処理剤を用いて電着処理されてなることを特徴とする電子部品。
（２）前記基材がチタン銅であることを特徴とする前記（１）に記載の電子部品。
（３）前記電着処理された後、リフロー処理されてなることを特徴とする前記（１）又は（２）に記載の電子部品。
（４）前記（１）～（３）のいずれか一項に記載の電子部品の製造方法であって、チタン銅またはコルソン合金からなる基材上に、Ｎｉめっき膜、Ｐｄ－Ｎｉめっき膜、ＡｕまたはＡｕ合金めっき膜の３層を順に形成し、ＡｕまたはＡｕ合金めっき膜表面に、インヒビターとして、ベンゾトリアゾール系化合物、メルカプトベンゾチアゾール系化合物、またはトリアジンチオール系化合物を含有する封孔処理剤を用いて電着処理することを特徴とする電子部品の製造方法。 As a result of intensive studies, the present inventors have found that the above problems can be solved by the following, and have reached the present invention.
That is, the present invention is as follows.
(1) On a substrate made of titanium copper or Corson alloy, there are three layers of Ni plating film, Pd—Ni plating film, Au or Au alloy plating film in order, and the surface of Au or Au alloy plating film is an inhibitor. An electronic component obtained by electrodeposition using a sealing agent containing a benzotriazole compound, a mercaptobenzothiazole compound, or a triazine thiol compound.
(2) The electronic component according to (1), wherein the base material is titanium copper.
(3) The electronic component according to (1) or (2), wherein the electronic component is subjected to a reflow process after the electrodeposition process.
(4) The method of manufacturing an electronic component according to any one of (1) to (3), wherein a Ni plating film, a Pd—Ni plating film, on a substrate made of titanium copper or a Corson alloy, Three layers of Au or Au alloy plating film are sequentially formed, and a sealing agent containing a benzotriazole compound, a mercaptobenzothiazole compound, or a triazine thiol compound as an inhibitor is formed on the Au or Au alloy plating film surface. A method of manufacturing an electronic component, wherein the electrodeposition treatment is performed.
　本発明によると、基材としてチタン銅やコルソン合金を用いＡｕまたはＡｕ合金めっき膜を有する電子部品において、ＡｕまたはＡｕ合金めっき膜が薄くてもピンホールの発生が少なく、チタン銅の腐食や変色が起こりにくく、耐食性に優れた電子部品、およびその製造方法を提供することができる。 According to the present invention, in an electronic component using titanium copper or a Corson alloy as a substrate and having an Au or Au alloy plating film, even if the Au or Au alloy plating film is thin, the occurrence of pinholes is small, and corrosion or discoloration of titanium copper is caused. Can be provided, and an electronic component having excellent corrosion resistance and a method for manufacturing the same can be provided.
実施例で行ったリフロー処理のプロファイルを示すグラフである。It is a graph which shows the profile of the reflow process performed in the Example.
　本発明の電子部品は、チタン銅またはコルソン合金からなる基材上に、Ｎｉめっき膜、Ｐｄ－Ｎｉめっき膜、ＡｕまたはＡｕ合金めっき膜の３層を有し、さらにＡｕまたはＡｕ合金めっき膜表面が、インヒビターとして、ベンゾトリアゾール系化合物、メルカプトベンゾチアゾール系化合物、またはトリアジンチオール系化合物を含有する封孔処理剤を用いて電着処理されてなる。
　本発明は、基材として、チタン銅またはコルソン合金を用いる。
　チタン銅は銅にチタンを１．０～４．０質量％添加した特殊銅合金であり、更に鉄等を含有していても良い。チタン銅は、強度、耐応力緩和特性、曲げ加工性においては、高強度・高機能銅合金の代表格であるベリリウム銅合金に匹敵する特性を有している。
　コルソン合金は銅を主成分とし、Ｎｉ、Ｓｉを主な副成分とする特殊銅合金の１種であり、更にマグネシウム、スズ、亜鉛、コバルト、クロム、マンガン等を含有しても良い。コルソン合金は、強度、電気伝導度が高く、曲げ加工性に優れる。 The electronic component of the present invention has three layers of a Ni plating film, a Pd—Ni plating film, and an Au or Au alloy plating film on a substrate made of titanium copper or a Corson alloy, and further the surface of the Au or Au alloy plating film. However, an electrodeposition treatment is performed using a sealing agent containing a benzotriazole compound, a mercaptobenzothiazole compound, or a triazine thiol compound as an inhibitor.
In the present invention, titanium copper or a Corson alloy is used as a base material.
Titanium copper is a special copper alloy obtained by adding 1.0 to 4.0% by mass of titanium to copper, and may further contain iron or the like. Titanium copper has properties comparable to beryllium copper alloys, which are typical of high strength and high function copper alloys, in strength, stress relaxation resistance and bending workability.
The Corson alloy is a kind of special copper alloy mainly composed of copper and mainly composed of Ni and Si, and may further contain magnesium, tin, zinc, cobalt, chromium, manganese and the like. Corson alloy has high strength and electrical conductivity, and is excellent in bending workability.
　しかし、これらの銅合金を基材として用いて、その上にＮｉめっき膜、Ａｕめっき膜を形成すると、チタン銅はチタンの酸化物が、コルソン合金はＳｉの酸化物が銅基材表面に顔を出すため、ニッケル下地めっきの密着性が悪く、めっき物の耐食性が悪くなった。
　本発明において、基材であるチタン銅またはコルソン合金の腐食／変色を防止する方法として、該基材上にＮｉめっき膜、Ｐｄ－Ｎｉめっき膜、ＡｕまたはＡｕ合金めっき膜の３層を形成する。
　基材上に、Ｎｉめっき膜と、Ｐｄ－Ｎｉめっき膜を形成することにより、Ｐｄ－Ｎｉ膜中に存在するピンホールを減らすことができ、基材が露出することを防ぐことができる。また、ＡｕまたはＡｕ合金めっき膜の厚さを薄くすることができる。 However, when these copper alloys are used as a base material and a Ni plating film or an Au plating film is formed thereon, titanium copper has titanium oxide, and Corson alloy has Si oxide on the copper base surface. Therefore, the adhesion of the nickel base plating was poor, and the corrosion resistance of the plated product was deteriorated.
In the present invention, as a method for preventing corrosion / discoloration of titanium copper or Corson alloy as a base material, three layers of Ni plating film, Pd—Ni plating film, Au or Au alloy plating film are formed on the base material. .
By forming the Ni plating film and the Pd—Ni plating film on the base material, pinholes existing in the Pd—Ni film can be reduced, and the base material can be prevented from being exposed. Further, the thickness of the Au or Au alloy plating film can be reduced.
　さらに、本発明の電子部品は、ＡｕまたはＡｕ合金めっき膜表面が、インヒビターとして、ベンゾトリアゾール系化合物、メルカプトベンゾチアゾール系化合物、またはトリアジンチオール系化合物を含有する封孔処理剤を用いて電着処理されてなることが重要である。特定のインヒビターを含有する封孔処理剤を用いて電着処理することにより、一層ピンホールを低減でき、基材の腐食、変色をより確実に防止することができる。
　封孔処理しない場合、また封孔処理が電着処理でない場合は、ピンホールを低減する効果が十分ではなく、基材が腐食、変色する。 Furthermore, in the electronic component of the present invention, the surface of the Au or Au alloy plating film is electrodeposited using a sealing agent containing a benzotriazole compound, a mercaptobenzothiazole compound, or a triazine thiol compound as an inhibitor. It is important to be made. By performing electrodeposition using a sealing agent containing a specific inhibitor, pinholes can be further reduced, and corrosion and discoloration of the substrate can be more reliably prevented.
When the sealing treatment is not performed or when the sealing treatment is not an electrodeposition treatment, the effect of reducing pinholes is not sufficient, and the substrate is corroded and discolored.
　また、前記ベンゾトリアゾール系化合物、メルカプトベンゾチアゾール系化合物、トリアジンチオール系化合物以外のインヒビターを用いた封孔処理剤や、前記インヒビターを用いた処理剤であっても浸漬処理を行った場合は、リフロー処理を行うと封孔処理の効果がなくなる。しかし、前記封孔処理剤を用いて電着処理することにより、よりピンホールの内部への処理が可能となるため、リフロー処理しても封孔処理の効果がなくなることはない。リフロー処理において、最高温度が２４０℃以上に加熱されても封孔処理の効果が維持される。本発明では、２８０℃まで、封孔処理の効果があることを確認している。 In addition, if a sealing treatment using an inhibitor other than the benzotriazole-based compound, mercaptobenzothiazole-based compound, or triazine thiol-based compound, or a treatment using the inhibitor, reflow is performed. When the treatment is performed, the effect of the sealing treatment is lost. However, the electrodeposition treatment using the sealing agent makes it possible to further process the inside of the pinhole. Therefore, even if the reflow treatment is performed, the effect of the sealing treatment is not lost. In the reflow process, the effect of the sealing process is maintained even when the maximum temperature is heated to 240 ° C. or higher. In the present invention, it is confirmed that there is an effect of sealing treatment up to 280 ° C.
　本発明の電子部品の製造方法は、チタン銅またはコルソン合金からなる基材上に、Ｎｉめっき膜、Ｐｄ－Ｎｉめっき膜、ＡｕまたはＡｕ合金めっき膜の３層を順に形成し、ＡｕまたはＡｕ合金めっき膜表面を、インヒビターとして、ベンゾトリアゾール系化合物、メルカプトベンゾチアゾール系化合物、またはトリアジンチオール系化合物を含有する封孔処理剤を用いて電着処理する。
　特にチタン銅は、強度、耐応力緩和特性、曲げ加工性においては、高強度・高機能銅合金の代表格であるベリリウム銅合金に匹敵する特性を有している。このため、基材としてチタン銅を用いた本発明の電子部品は、パソコンや携帯電話等の電子機器の主にコネクタ端子、バッテリー端子、バーンインソケット等の用途で好適に用いることができる。 The method for manufacturing an electronic component according to the present invention includes forming three layers of a Ni plating film, a Pd—Ni plating film, Au or an Au alloy plating film in this order on a substrate made of titanium copper or a Corson alloy, and Au or Au alloy. The plating film surface is subjected to electrodeposition treatment using a sealing agent containing a benzotriazole compound, mercaptobenzothiazole compound, or triazine thiol compound as an inhibitor.
In particular, titanium copper has characteristics comparable to beryllium copper alloys, which are typical of high-strength and high-function copper alloys, in strength, stress relaxation resistance, and bending workability. For this reason, the electronic component of the present invention using titanium copper as a base material can be suitably used mainly for applications such as connector terminals, battery terminals, and burn-in sockets of electronic devices such as personal computers and mobile phones.
　前記Ｎｉめっき膜は、電解めっきにより形成することが好ましく、電解Ｎｉめっき液としては、電子部品の製造に用いられる公知のめっき液を用いることができる。例えば、スルファミン酸浴、ワット浴等のＮｉめっき液を好ましく用いることができる。
　Ｎｉめっき条件も公知のめっき条件でよい。
　Ｎｉめっき膜の厚さは０．５～５μｍが好ましい。 The Ni plating film is preferably formed by electrolytic plating. As the electrolytic Ni plating solution, a known plating solution used for manufacturing electronic components can be used. For example, a Ni plating solution such as a sulfamic acid bath or a watt bath can be preferably used.
Ni plating conditions may also be known plating conditions.
The thickness of the Ni plating film is preferably 0.5 to 5 μm.
　Ｐｄ－Ｎｉめっき膜は、電解めっきにより形成することが好ましく、電解Ｐｄ－Ｎｉめっき液としては、電子部品の製造に用いられる公知のめっき液を用いることができる。例えば、アンモニア浴等のＰｄ－Ｎｉめっき液を好ましく用いることができる。
　Ｐｄ－Ｎｉめっき膜は、Ｎｉを５～５０質量％含有することが好ましい。
　Ｐｄ－Ｎｉめっき条件も公知のめっき条件でよい。
　また、Ｐｄ－Ｎｉめっき膜の厚さは０．０５～１μｍが好ましい。 The Pd—Ni plating film is preferably formed by electrolytic plating. As the electrolytic Pd—Ni plating solution, a known plating solution used for manufacturing electronic components can be used. For example, a Pd—Ni plating solution such as an ammonia bath can be preferably used.
The Pd—Ni plating film preferably contains 5 to 50% by mass of Ni.
The Pd—Ni plating conditions may also be known plating conditions.
The thickness of the Pd—Ni plating film is preferably 0.05 to 1 μm.
　ＡｕまたはＡｕ合金めっき膜は、電解めっきにより形成することが好ましく、電解Ａｕめっき液、Ａｕ合金めっき液としては、電子部品の製造に用いられる公知のめっき液を用いることができる。弱酸性タイプのＡｕめっき液、Ａｕ－Ｃｏ系合金（Ｃｏ　０．２～０．５質量％）めっきが好ましく、例えば、クエン酸浴のめっき液を好ましく用いることができる。
　Ａｕめっき、Ａｕ合金めっきの条件も公知のめっき条件でよい。
　ＡｕまたはＡｕ合金めっき膜の厚さは０．０１～０．１μｍが好ましい。 The Au or Au alloy plating film is preferably formed by electrolytic plating. As the electrolytic Au plating solution and the Au alloy plating solution, a known plating solution used for manufacturing electronic components can be used. Weakly acidic type Au plating solution and Au—Co alloy (Co 0.2 to 0.5 mass%) plating are preferable. For example, a citric acid bath plating solution can be preferably used.
The conditions for Au plating and Au alloy plating may be known plating conditions.
The thickness of the Au or Au alloy plating film is preferably 0.01 to 0.1 μm.
　本発明の電子部品は、Ａｕめっき膜上に封孔処理剤を用いて電着処理を行ったものである。封孔処理剤としては、インヒビターとしてベンゾトリアゾール系化合物、メルカプトベンゾチアゾール系化合物、またはトリアジンチオール系化合物を含有する封孔処理剤を用いる。 The electronic component of the present invention is obtained by performing an electrodeposition treatment using a sealing agent on an Au plating film. As the sealing agent, a sealing agent containing a benzotriazole compound, a mercaptobenzothiazole compound, or a triazine thiol compound as an inhibitor is used.
　前記ベンゾトリアゾール系化合物は下記一般式（１）
Figure JPOXMLDOC01-appb-C000001
 （式中、Ｒ1は水素、アルキル、置換アルキルを表わし、Ｒ2はアルカリ金属、水素、アルキル、置換アルキルを表わす）
で表わされる。
　この一般式（１）で表わされる化合物のうち好ましいものを挙げると、例えば、１Ｈベンゾトリアゾール（Ｒ1，Ｒ2とも水素）、１－メチルベンゾトリアゾール（Ｒ1が水素、Ｒ2がメチル）、トリルトリアゾール（Ｒ1がメチル、Ｒ2が水素）、１－（Ｎ，Ｎ－ジオクチルアミノメチル）ベンゾトリアゾール（Ｒ1が水素、Ｒ2がＮ，Ｎ－ジオクチルアミノメチル）などである。 The benzotriazole-based compound has the following general formula (1)
Figure JPOXMLDOC01-appb-C000001
 (Wherein R 1 represents hydrogen, alkyl, or substituted alkyl, and R 2 represents an alkali metal, hydrogen, alkyl, or substituted alkyl)
It is represented by
Preferred examples of the compound represented by the general formula (1) include 1H benzotriazole (both R 1 and R 2 are hydrogen), 1-methylbenzotriazole (R 1 is hydrogen, R 2 is methyl), Tolyltriazole (R 1 is methyl, R 2 is hydrogen), 1- (N, N-dioctylaminomethyl) benzotriazole (R 1 is hydrogen, R 2 is N, N-dioctylaminomethyl) and the like.
　前記メルカプトベンゾチアゾール系化合物は一般式（２）
Figure JPOXMLDOC01-appb-C000002
 （式中、Ｒ3はアルカリ金属又は水素を表わす）
で表わされる。
　この一般式（２）で表わされる化合物のうち好ましいものを挙げると、例えば２－メルカプトベンゾチアゾール、２－メルカプトベンゾチアゾールのナトリウム塩、２－メルカプトベンゾチアゾールのカリウム塩などがある。
　一般式（２）においてＲ3がアルカリ金属の場合メルカプトベンゾチアゾール系化合物の水への溶解が容易となる。 The mercaptobenzothiazole compound has the general formula (2)
Figure JPOXMLDOC01-appb-C000002
 (Wherein R 3 represents an alkali metal or hydrogen)
It is represented by
Preferred examples of the compound represented by the general formula (2) include 2-mercaptobenzothiazole, sodium salt of 2-mercaptobenzothiazole, and potassium salt of 2-mercaptobenzothiazole.
In the general formula (2), when R 3 is an alkali metal, the mercaptobenzothiazole compound is easily dissolved in water.
　トリアジンチオール系化合物は一般式（３）
Figure JPOXMLDOC01-appb-C000003
 〔式中、Ｒ4は－ＳＨ、アルキル基かアリール基で置換されたアミノ基、又はアルキル置換イミダゾリルアルキル、Ｒ5、Ｒ6は－ＮＨ2、－ＳＨ又は－ＳＭ（Ｍはアルカリ金属を表わす）を表わす。ただし、前記Ｒ4、Ｒ5、Ｒ6のうち少なくともいずれか１つは－ＳＨ又は－ＳＭである。〕
で表わされる。
　この一般式（３）で表わされる化合物のうち好ましいものを挙げると例えば以下のものがある。 Triazine thiol compounds are represented by the general formula (3)
Figure JPOXMLDOC01-appb-C000003
 [Wherein R 4 is —SH, an amino group substituted with an alkyl group or an aryl group, or an alkyl-substituted imidazolylalkyl, R 5 , R 6 are —NH 2 , —SH or —SM (M represents an alkali metal) ). However, at least one of R 4 , R 5 and R 6 is —SH or —SM. ]
It is represented by
Preferred examples of the compound represented by the general formula (3) include the following.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　あるいはこれらのＮａまたはＫなどのアルカリ金属塩がある。一般式（３）においてＲ5，Ｒ6が－ＳＭである場合にはトリアジンチオール系化合物の水への溶解が容易となる。 Alternatively, there are alkali metal salts such as Na or K. In the general formula (3), when R 5 and R 6 are —SM, the triazine thiol compound can be easily dissolved in water.
　インヒビターの添加量は０．００１～１ｗｔ％の範囲であり、０．００１ｗｔ％未満では封孔処理効果が認められず、１ｗｔ％を越えると接触抵抗への悪影響が認められる。 The addition amount of the inhibitor is in the range of 0.001 to 1 wt%. If it is less than 0.001 wt%, the sealing treatment effect is not observed, and if it exceeds 1 wt%, an adverse effect on the contact resistance is recognized.
　本発明の封孔処理に用いる処理剤は、更に潤滑剤を含有しても良い。潤滑剤としては、脂肪酸が好ましく、封孔処理剤に添加することにより、金めっき材の潤滑性向上に寄与する。
　前記脂肪酸としては、例えばラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸などが挙げられる。
　潤滑剤の添加量は０．０５ｗｔ％～２ｗｔ％の範囲が好ましい。０．０５ｗｔ％未満では潤滑効果が得られにくく、２ｗｔ％を越えると封孔処理後の材料の外観への悪影響が認められる。 The processing agent used for the sealing treatment of the present invention may further contain a lubricant. The lubricant is preferably a fatty acid, and contributes to improving the lubricity of the gold plating material by adding to the sealing agent.
Examples of the fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid.
The amount of lubricant added is preferably in the range of 0.05 wt% to 2 wt%. If it is less than 0.05 wt%, it is difficult to obtain a lubricating effect, and if it exceeds 2 wt%, an adverse effect on the appearance of the material after the sealing treatment is observed.
　本発明の封孔処理に用いる処理剤は、乳化剤を含有しても良く、乳化剤としては、モノアルキルリン酸エステル、ジアルキルリン酸エステルが好ましい。乳化剤は、処理剤に添加され、潤滑剤の乳化剤としての機能をはたす。さらに乳化剤には潤滑作用もある。
　前記モノアルキルリン酸エステル、ジアルキルリン酸エステルは、リン酸と脂肪族アルコールを脱水縮合したものであり、該脂肪族アルコールとしては、例えばデシルアルコール、ラウリルアルコール、ミリスチルアルコール、セタノール、ステアリルアルコールなどが好ましい。
　これらは、モノエステルでもジエステルでも良く、それぞれ単独で用いても良いが、モノエステルとジエステルの混合物や、アルコール成分が異なる複数のリン酸エステルの混合物を用いても良く、これらの混合比も問わない。これらのモノアルキルリン酸エステル、ジアルキルリン酸エステルとしては、市販品を用いることができる。
　乳化剤の添加量は０．０５ｗｔ～２ｗｔ％の範囲であり、０．０５ｗｔ％未満では乳化効果が得られにくく、２ｗｔ％を越えるとはんだ付け性への悪影響が認められる。 The processing agent used for the sealing treatment of the present invention may contain an emulsifier, and the emulsifier is preferably a monoalkyl phosphate ester or a dialkyl phosphate ester. The emulsifier is added to the treating agent and functions as an emulsifier for the lubricant. Furthermore, the emulsifier also has a lubricating action.
The monoalkyl phosphate ester and dialkyl phosphate ester are obtained by dehydration condensation of phosphoric acid and an aliphatic alcohol. Examples of the aliphatic alcohol include decyl alcohol, lauryl alcohol, myristyl alcohol, cetanol, and stearyl alcohol. preferable.
These may be monoesters or diesters, and each may be used alone, but a mixture of monoesters and diesters or a mixture of a plurality of phosphate esters having different alcohol components may be used. Absent. As these monoalkyl phosphate esters and dialkyl phosphate esters, commercially available products can be used.
The added amount of the emulsifier is in the range of 0.05 wt% to 2 wt%. If it is less than 0.05 wt%, the emulsifying effect is difficult to obtain, and if it exceeds 2 wt%, an adverse effect on solderability is observed.
　封孔処理液は上述の成分を有する水溶液であるが、溶液の温度は１０～８０℃が好ましく、３０～５０℃がより好ましい。１０～８０℃にすることにより、成分の水への乳化がより速やかに進行し、さらに封孔処理後の材料の乾燥が容易になる。
　処理方法としては、めっき品を処理液中に浸漬させ、材料を陽極として極間に直流またはパルス電流を流して行う。めっき品を陽極にすることにより、溶液中のインヒビターはめっき品のピンホール内部の下地金属に吸着し、その腐食を防止する。電流密度は０．１ｍＡ／ｄｍ2以上であることが好ましく、１～１００ｍＡ／ｄｍ2がより好ましい。０．１ｍＡ／ｄｍ2未満では封孔処理効果が得られない。処理時間は１～１０秒が望ましい。また、電流密度と処理時間の積が１０～１０００ｍＡ・ｓｅｃ／ｄｍ2であることが好ましく、２０～２００ｍＡ・ｓｅｃ／ｄｍ2であることがより好ましい。 The sealing treatment liquid is an aqueous solution having the above components, and the temperature of the solution is preferably 10 to 80 ° C., more preferably 30 to 50 ° C. By setting the temperature to 10 to 80 ° C., the emulsification of the components in water proceeds more rapidly, and the material after the sealing treatment can be easily dried.
As a treatment method, a plated product is immersed in a treatment solution, and a direct current or a pulse current is passed between the electrodes using the material as an anode. By using the plated product as an anode, the inhibitor in the solution is adsorbed to the base metal inside the pinhole of the plated product and prevents its corrosion. The current density is preferably 0.1 mA / dm 2 or more, more preferably 1 to 100 mA / dm 2 . If it is less than 0.1 mA / dm 2 , the sealing treatment effect cannot be obtained. The processing time is preferably 1 to 10 seconds. The product of the current density and the processing time is preferably 10 to 1000 mA · sec / dm 2 , more preferably 20 to 200 mA · sec / dm 2 .
　本発明の電子部品としては、電子機器用接続部品であるコネクタ等が挙げられる。特にばね性や耐摩耗性がより求められるバッテリー端子用コネクタに好適に用いることができる。 The electronic component of the present invention includes a connector that is a connecting component for electronic equipment. In particular, it can be suitably used for a battery terminal connector that requires more springiness and wear resistance.
　以下に示す実施例及び比較例により更に本発明を説明する。
実施例１～５、及び比較例１～３：
　チタン銅材（ＮＫＴ３２２，２５ｍｍ×２０ｍｍ×０．２ｍｍｔ）、もしくはコルソン合金材（Ｃ７０２５，２５ｍｍ×２０ｍｍ×０．２ｍｍｔ）に、スルファミン酸浴により、全面に電解ニッケルめっきを３μｍ行なった後、アンモニア浴により、電解Ｐｄ－Ｎｉ合金めっき（Ｐｄ／Ｎｉ＝８／２（質量比））を０．２μｍ行い、その後、クエン酸浴で、電解金めっきを０．０５μｍ行なっためっき基板を供試材とした。
　チタン銅を基材としためっき基板を表１の実施例１～４、または比較例３の条件で電着により封孔処理し、十分に水洗した後、ドライヤーで乾燥することにより、封孔処理剤被膜を形成させた。また、コルソン合金を基材としためっき基板を実施例５の条件で同様に電着により封孔処理被膜を形成させた。比較例１はチタン銅を基材としためっき基板に封孔処理を行わなかったものである。比較例２は、チタン銅を基材としためっき基板に封孔処理を浸漬処理により行ったものである。
　なお、封孔処理剤の溶媒にはイオン交換水を用いた。また、封孔処理剤に用いたラウリルリン酸エステル、デシルリン酸エステルは、モノエステルとジエステルとの混合物である。 The following examples and comparative examples further illustrate the present invention.
Examples 1 to 5 and Comparative Examples 1 to 3:
Titanium copper material (NKT322, 25 mm x 20 mm x 0.2 mmt) or Corson alloy material (C7025, 25 mm x 20 mm x 0.2 mmt) is subjected to electrolytic nickel plating on the entire surface with a sulfamic acid bath for 3 μm, and then an ammonia bath Then, a plated substrate on which electrolytic Pd—Ni alloy plating (Pd / Ni = 8/2 (mass ratio)) was performed by 0.2 μm and electrolytic gold plating was performed by 0.05 μm in a citric acid bath was used as a test material. did.
The plated substrate based on titanium copper was subjected to sealing treatment by electrodeposition under the conditions of Examples 1 to 4 or Comparative Example 3 in Table 1, sufficiently washed with water, and then dried with a drier to seal the plating. An agent film was formed. Further, a sealing treatment film was formed on the plated substrate based on the Corson alloy by the same electrodeposition under the conditions of Example 5. In Comparative Example 1, sealing treatment was not performed on a plated substrate based on titanium copper. In Comparative Example 2, sealing treatment was performed by dipping treatment on a plated substrate based on titanium copper.
In addition, ion-exchange water was used for the solvent of the sealing agent. Moreover, the lauryl phosphate ester and decyl phosphate ester used for the sealing agent are a mixture of a monoester and a diester.
　得られた基板に対し、図１に示すプロファイルでリフロー処理（大気雰囲気）を行った後、塩水噴霧試験（ＪＩＳＺ２３７１準拠）を７２時間行い、耐食性の評価を行った。結果を表１に示す。
　評価基準：
　　○：ほとんど腐食なし。
　　△：所々に黒点状の腐食が見られる。
　　×：所々に茶褐色及び／または緑色の腐食点が見られる。 The obtained substrate was subjected to reflow treatment (atmospheric atmosphere) with the profile shown in FIG. 1 and then subjected to a salt spray test (based on JISZ2371) for 72 hours to evaluate corrosion resistance. The results are shown in Table 1.
Evaluation criteria:
○: Almost no corrosion.
Δ: Black spot-like corrosion is observed in some places.
X: A brown and / or green corrosion point is observed in some places.
　尚、比較例３は、本発明に係る封孔処理剤とは異なった封孔処理剤を用いた例である。比較例３で用いた封孔処理剤は、基材としてリン青銅（Ｃ５２１０，２５ｍｍ×２０ｍｍ×０．２ｍｍｔ）を用いた場合は、耐食性の効果が得られることを確認している。即ち、比較例３は、リン青銅基材に有効な封孔処理剤がそのまま同様にチタン銅基材の封孔処理に有効とはならないことを示すものである。 In addition, the comparative example 3 is an example using the sealing agent different from the sealing agent concerning this invention. The sealing agent used in Comparative Example 3 has been confirmed to have an effect of corrosion resistance when phosphor bronze (C5210, 25 mm × 20 mm × 0.2 mmt) is used as a base material. That is, Comparative Example 3 shows that a sealing agent effective for a phosphor bronze base material is not effective for sealing a titanium copper base material as it is.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006

Claims (4)

  1. 　チタン銅またはコルソン合金からなる基材上に、Ｎｉめっき膜、Ｐｄ－Ｎｉめっき膜、ＡｕまたはＡｕ合金めっき膜の３層を順に有し、さらにＡｕまたはＡｕ合金めっき膜表面が、インヒビターとして、ベンゾトリアゾール系化合物、メルカプトベンゾチアゾール系化合物、またはトリアジンチオール系化合物を含有する封孔処理剤を用いて電着処理されてなることを特徴とする電子部品。 On the base material made of titanium copper or Corson alloy, there are three layers of Ni plating film, Pd—Ni plating film, Au or Au alloy plating film in order, and the Au or Au alloy plating film surface has benzoate as an inhibitor. An electronic component obtained by electrodeposition using a sealing agent containing a triazole compound, a mercaptobenzothiazole compound, or a triazine thiol compound.
  2. 　前記基材がチタン銅であることを特徴とする請求項１に記載の電子部品。 The electronic component according to claim 1, wherein the base material is titanium copper.
  3. 　前記電着処理された後、リフロー処理されてなることを特徴とする請求項１又は２に記載の電子部品。 The electronic component according to claim 1, wherein the electronic component is subjected to a reflow process after the electrodeposition process.
  4. 　請求項１～３のいずれか一項に記載の電子部品の製造方法であって、チタン銅またはコルソン合金からなる基材上に、Ｎｉめっき膜、Ｐｄ－Ｎｉめっき膜、ＡｕまたはＡｕ合金めっき膜の３層を順に形成し、ＡｕまたはＡｕ合金めっき膜表面に、インヒビターとして、ベンゾトリアゾール系化合物、メルカプトベンゾチアゾール系化合物、またはトリアジンチオール系化合物を含有する封孔処理剤を用いて電着処理することを特徴とする電子部品の製造方法。 4. The method of manufacturing an electronic component according to claim 1, wherein a Ni plating film, a Pd—Ni plating film, an Au or Au alloy plating film is formed on a substrate made of titanium copper or a Corson alloy. Are sequentially formed, and electrodeposition treatment is performed on the Au or Au alloy plating film surface using a sealing agent containing a benzotriazole compound, a mercaptobenzothiazole compound, or a triazine thiol compound as an inhibitor. An electronic component manufacturing method characterized by the above.
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US20200117125A1 (en) * 2018-10-10 2020-04-16 Yuusuke Furuichi Heating device, fixing device, and image forming apparatus
US10775726B2 (en) 2018-10-10 2020-09-15 Ricoh Company, Ltd. Image forming apparatus with a heating device having a feeding member on a non-driving side of a driving roller
US10845740B2 (en) 2018-12-07 2020-11-24 Ricoh Company, Ltd. Temperature detector, heating device, fixing device, and image forming apparatus
WO2020158679A1 (en) * 2019-01-29 2020-08-06 ダイキン工業株式会社 Method for inspecting refrigerant pipe and refrigerant pipe
JP2020122684A (en) * 2019-01-29 2020-08-13 ダイキン工業株式会社 Inspection method of refrigerant pipe and refrigerant pipe

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