JP2017082297A - Method for forming metal film on surface of copper-containing base material - Google Patents
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Abstract
Description
本発明は、Ｚｎ、Ｍｇ、Ｎｉのいずれか１つ以上を含む銅含有基材表面に金属膜を形成する方法に関する。 The present invention relates to a method for forming a metal film on the surface of a copper-containing substrate containing any one or more of Zn, Mg, and Ni.
従来より、銅含有基材の表面に局所的なメッキを施す方法として、導電性の良い金の導電性ナノ粒子を含む金属ナノインクを銅含有基材の表面に塗布して金属ナノインク層を形成し、このインク層の溶媒を除去した後、このインク層にレーザ光を照射することにより、インク層を焼成して、銅含有基材表面にメッキを施す技術が提案されている（例えば、特許文献１参照。）。 Conventionally, as a method of locally plating the surface of a copper-containing substrate, a metal nano ink containing gold conductive nanoparticles having good conductivity is applied to the surface of the copper-containing substrate to form a metal nano ink layer. Then, after removing the solvent of the ink layer, a technique for firing the ink layer by irradiating the ink layer with a laser beam and plating the surface of the copper-containing substrate has been proposed (for example, Patent Documents). 1).
特許文献１には、銅含有基材として、車両用ハーネス等のコネクタ等に内蔵される銅合金からなる端子金具が例示される。特許文献１に示される発明では、長尺の帯状板材を端子金具の展開状態に連続して打ち抜き、打ち抜かれた展開状態の端子金具の表面に金粒子インクをインクジェット装置で塗布し、溶媒を除去し、パルスレーザビーム照射による熱処理で金粒子を焼結させてメッキを施した後、上記展開状態の端子金具の折り曲げ加工を行って所望の端子金具に製造している。 Patent Document 1 exemplifies a terminal fitting made of a copper alloy built in a connector such as a vehicle harness as the copper-containing base material. In the invention disclosed in Patent Document 1, a long strip-shaped plate material is continuously punched in a developed state of a terminal fitting, and gold particle ink is applied to the surface of the punched-out terminal fitting by an inkjet device to remove the solvent. After the gold particles are sintered by heat treatment by pulse laser beam irradiation and plated, the developed terminal fitting is bent to produce a desired terminal fitting.
しかし、上記特許文献１に示されるメッキを施した後、上記展開状態の端子金具をメッキ膜である金属膜を形成した箇所の近傍で折り曲げ加工を行うと、金属膜の近傍にクラックが発生したり、金属膜が剥離することがあり、未だ解決すべき問題点があった。 However, after the plating shown in Patent Document 1 is performed, if the terminal fitting in the expanded state is bent in the vicinity of the place where the metal film as the plating film is formed, a crack is generated in the vicinity of the metal film. In some cases, the metal film may peel off, and there are still problems to be solved.
本発明の目的は、金属膜を形成した銅含有基材の金属膜形成箇所近傍で折り曲げ加工したときに基材にクラックを発生せず、金属膜が剥離しない、銅含有基材表面に金属膜を形成する方法を提供することにある。 The object of the present invention is to prevent a metal film from being cracked and peeled off when the metal film is formed in the vicinity of the metal film forming portion of the copper-containing base material on which the metal film is formed. It is in providing the method of forming.
本発明者らは、従来の課題である銅含有基材でのクラックと金属膜の剥離が発生する原因を鋭意研究したところ、レーザ光照射のような局所加熱に対して、銅含有基材の耐久性が十分でないことを突き止め、本発明に到達した。 The present inventors diligently studied the cause of cracking and peeling of a metal film in a copper-containing base material, which is a conventional problem, and as a result of local heating such as laser light irradiation, Ascertaining that the durability is not sufficient, the present invention has been reached.
本発明の第１の観点は、Ｚｎ、Ｍｇ、Ｎｉのいずれか１つ以上を含む銅含有基材の表面に金インクを塗布して金インク層を形成し、前記インク層の溶媒を除去した後、前記基材表面から前記インク層にレーザ光照射、マイクロ波照射、赤外線照射又は光焼成による光照射のいずれかの熱処理を施すことにより、前記インク層を焼成して銅含有基材表面に金属膜を形成する方法である。 According to a first aspect of the present invention, a gold ink layer is formed on a surface of a copper-containing substrate containing at least one of Zn, Mg, and Ni to form a gold ink layer, and the solvent of the ink layer is removed. Thereafter, the ink layer is baked on the surface of the copper-containing substrate by performing any one of heat treatment of laser irradiation, microwave irradiation, infrared irradiation, or light irradiation by light baking from the substrate surface to the ink layer. This is a method of forming a metal film.
本発明の第２の観点は、第１の観点に基づく発明であって、前記金インクが、金レジネートインク、金ナノインク又は金錯体インクのいずれか一つ以上を含む金属膜の形成方法である。 A second aspect of the present invention is a method of forming a metal film according to the first aspect, wherein the gold ink includes one or more of a gold resinate ink, a gold nano ink, or a gold complex ink. .
本発明の第３の観点は、第２の観点に基づく発明であって、前記金ナノインクが、平均粒径が１００ｎｍ以下の金ナノ粒子を含む金属膜の形成方法である。 A third aspect of the present invention is an invention based on the second aspect, wherein the gold nanoink is a method for forming a metal film containing gold nanoparticles having an average particle diameter of 100 nm or less.
本発明の第４の観点は、第１ないし第３のいずれかの観点に基づく発明であって、前記銅含有基材がＺｎ、Ｍｇ、Ｎｉのいずれか１つ以上を含む銅合金の端子金具である金属膜の形成方法である。 A fourth aspect of the present invention is an invention based on any one of the first to third aspects, wherein the copper-containing base material includes a copper alloy terminal fitting including at least one of Zn, Mg, and Ni. This is a method for forming a metal film.
本発明の第１の観点の金属膜の形成方法では、銅含有基材として、Ｚｎ、Ｍｇ、Ｎｉのいずれか１つ以上を含む材料を用いることにより、高い耐熱性を有するために、金属膜を形成した銅含有基材の金属膜形成箇所近傍で折り曲げ加工したときに基材にクラックを発生せず、金属膜が剥離しない優れた効果を奏した。 In the method for forming a metal film according to the first aspect of the present invention, the metal film has high heat resistance by using a material containing any one or more of Zn, Mg, and Ni as the copper-containing substrate. When the copper-containing base material in which the copper film was formed was bent in the vicinity of the metal film forming portion, the base material was not cracked and the metal film was not peeled off.
本発明の第２の観点の金属膜の形成方法では、金インクとして、金レジネートインク、金ナノインク又は金錯体インクのいずれか一つ以上のインクを用いることにより、銅含有基材表面の酸化防止に優れた金膜を形成することができる。 In the method for forming a metal film according to the second aspect of the present invention, by using at least one of gold resinate ink, gold nanoink, and gold complex ink as the gold ink, the oxidation of the copper-containing substrate surface is prevented. An excellent gold film can be formed.
本発明の第３の観点の金属膜の形成方法では、金ナノインクが金ナノ粒子を含むことにより、より緻密で強度の高い金属膜を形成することができる。 In the method for forming a metal film according to the third aspect of the present invention, the gold nano ink contains gold nanoparticles, whereby a denser and stronger metal film can be formed.
本発明の第４の観点の金属膜の形成方法では、銅含有基材を、民生用機器、産業用機器、自動車用機器等の銅又は銅合金の端子金具に用いれば、端子金具の金属膜を有する接点部分の信頼性を向上させることができる。 In the method for forming a metal film according to the fourth aspect of the present invention, if the copper-containing substrate is used for a copper or copper alloy terminal metal fitting for consumer equipment, industrial equipment, automobile equipment, etc., the metal film of the terminal fitting It is possible to improve the reliability of the contact portion having the.
次に本発明を実施するための形態を説明する。 Next, the form for implementing this invention is demonstrated.
本発明の金属膜の形成方法は、先ずＺｎ、Ｍｇ、Ｎｉのいずれか１つ以上を含む銅含有基材の表面に金インクを塗布して金インク層を形成する。銅含有基材としては、Ｚｎ、Ｍｇ、Ｎｉのいずれか１つ以上を含む銅又は銅合金からなる基材以外に、この基材表面にニッケルめっきが施されたものが挙げられる。基材は基板が好ましいが、基板に限らない。Ｚｎ、Ｍｇ、Ｎｉのいずれか１つ以上を含む銅含有基材としては、Ｃｕ９９質量％以上、Ｍｇ０．９質量％以下の銅条（三菱伸銅社製、製品名：ＭＳＰ１）が例示される。またＣｕ９５質量％以上、Ｚｎ１．５質量％以下、Ｎｉ２．７質量％以下、Ｍｇ０．２質量％以下の銅条（三菱伸銅社製、製品名：ＭＡＸ２５１）が例示される。またＣｕ９４質量％以上、Ｚｎ１．０質量％以下、Ｎｉ３．０質量％以下、Ｍｇ０．２質量％以下の銅条（三菱伸銅社製、製品名：ＭＡＸ２５２）が例示される。またＣｕ９７質量％以上、Ｍｇ１．９％以下の銅条（三菱伸銅社製、製品名：ＭＳＰ５）が例示される。更にＣｕ８６質量％以上、Ｚｎ１２質量％以下、Ｎｉ０．８質量％以下の銅条（三菱伸銅社製、製品名：ＭＮＥＸ１０）が例示される。好ましいＺｎの含有量は０．５〜１０質量％であり、好ましいＭｇの含有量は０．１〜０．８質量％であり、好ましいＮｉの含有量は０．５〜２．８質量％である。銅含有基材として、Ｚｎ、Ｍｇ、Ｎｉのいずれか１つ以上を含む材料を用いることにより、高い耐熱性を有するために、金属膜を形成した銅含有基材の金属膜形成箇所近傍で折り曲げ加工したときに基材にクラックを発生せず、金属膜が剥離しない。 In the method for forming a metal film of the present invention, a gold ink layer is first formed by applying gold ink to the surface of a copper-containing substrate containing any one or more of Zn, Mg, and Ni. Examples of the copper-containing substrate include those obtained by applying nickel plating to the surface of the substrate other than a substrate made of copper or a copper alloy containing any one or more of Zn, Mg, and Ni. The substrate is preferably a substrate, but is not limited to a substrate. Examples of the copper-containing substrate containing at least one of Zn, Mg, and Ni include Cu strips of 99% by mass or more and 0.9% by mass or less of Mg (product name: MSP1 manufactured by Mitsubishi Shindoh Co., Ltd.). . Moreover, Cu 95 mass% or more, Zn 1.5 mass% or less, Ni 2.7 mass% or less, Mg 0.2 mass% or less copper strip (product name: MAX251 by Mitsubishi Shindoh Co., Ltd.) is illustrated. Moreover, the copper strip (product name: MAX252 by Mitsubishi Shindoh Co., Ltd.) of Cu 94 mass% or more, Zn 1.0 mass% or less, Ni 3.0 mass% or less, and Mg 0.2 mass% or less is illustrated. Moreover, the copper strip (made by Mitsubishi Shindoh Co., Ltd., product name: MSP5) of Cu 97 mass% or more and Mg 1.9% or less is illustrated. Furthermore, Cu 86 mass% or more, Zn 12 mass% or less, and Ni 0.8 mass% or less copper strip (product name: MNEX10, manufactured by Mitsubishi Shindoh Co., Ltd.) are exemplified. The preferable Zn content is 0.5 to 10% by mass, the preferable Mg content is 0.1 to 0.8% by mass, and the preferable Ni content is 0.5 to 2.8% by mass. is there. In order to have high heat resistance by using a material containing any one or more of Zn, Mg, and Ni as a copper-containing base material, it is bent in the vicinity of the metal film forming portion of the copper-containing base material on which the metal film is formed. When processed, the substrate does not crack and the metal film does not peel off.
金インクとしては、金レジネートインク、金ナノインク又は金錯体インクのいずれか一つ以上を含むインクが例示される。金インクは、金の有機化合物である金レジネート、金ナノ粒子又は金錯体のいずれか一つ以上を含むインクと溶媒を含む。金インクは、還元剤を更に含むことが好ましい。この還元剤としては、ギ酸又はアスコルビン酸が挙げられる。金ナノ粒子は平均粒径が１００ｎｍ以下であることが好ましい。金錯体としては、メチルトリメチルホスフィン金、ジメチル金(III)アセチルアセトナート、ジメチル金(III)トリフルオロアセチルアセトナート等が例示される。また、本発明の塗布物は、金レジネートインクに更に平均粒径が１００ｎｍ以下の金ナノ粒子を含んでもよい。金ナノ粒子を含ませることにより、より緻密で強度の高い金属膜を形成することができる。 Examples of the gold ink include ink containing one or more of gold resinate ink, gold nano ink, and gold complex ink. The gold ink includes an ink and a solvent containing any one or more of gold resinate, gold nanoparticles, and gold complex, which are gold organic compounds. The gold ink preferably further contains a reducing agent. Examples of the reducing agent include formic acid and ascorbic acid. The gold nanoparticles preferably have an average particle size of 100 nm or less. Examples of the gold complex include methyltrimethylphosphine gold, dimethylgold (III) acetylacetonate, dimethylgold (III) trifluoroacetylacetonate and the like. The coated product of the present invention may further contain gold nanoparticles having an average particle size of 100 nm or less in the gold resinate ink. By including gold nanoparticles, a denser and stronger metal film can be formed.
金レジネートとしては、α―ピネン、α―ターピネオール又はイソボルネオールのメルカプタン金、サルフィド金、アベチエン酸金、ネオデカン酸金、２−エチルヘキサン酸金及びナフテン酸金からなる群より選ばれた１種又は２種以上のレジネートが例示される。有機溶媒としては、α―ターピネオール、ブチルカルビトールアセテート、イソブタノール等が例示される。銅含有基材表面に金属レジネートインクを塗布する方法としては、スクリーン印刷法、インクジェット印刷法、ディスペンサ印刷法等が挙げられる。 As the gold resinate, one kind selected from the group consisting of mercaptan gold of α-pinene, α-terpineol or isoborneol, sulfide gold, gold abetienoate, gold neodecanoate, gold 2-ethylhexanoate and gold naphthenate or Two or more resinates are exemplified. Examples of the organic solvent include α-terpineol, butyl carbitol acetate, isobutanol and the like. Examples of the method for applying the metal resinate ink to the surface of the copper-containing substrate include a screen printing method, an ink jet printing method, a dispenser printing method, and the like.
金インクを塗布して金インク層を形成した後、このインク層の溶媒を除去する。インク層の溶媒の除去方法としては、基板をヒータ、ホットプレート等により強制的に加熱乾燥するか、加熱せずに放置し風乾する方法が挙げられる。溶媒を除去した後、前記基材表面から前記インク層に対して熱処理してこのインク層を焼成することにより金属膜を形成する。この熱処理方法としては、レーザ光照射、マイクロ波照射、赤外線照射又は光焼成による光照射の方法が挙げられる。インク層を局所的に熱処理可能なレーザ光照射又は光焼成が好ましい。なお、熱処理は、大気雰囲気、不活性ガス雰囲気等で行うことができるが、大気雰囲気で行うことが好ましい。 After gold ink is applied to form a gold ink layer, the solvent of this ink layer is removed. Examples of the method for removing the solvent of the ink layer include a method in which the substrate is forcibly heated and dried with a heater, a hot plate, or the like, or left without being heated and air-dried. After removing the solvent, the ink layer is heat-treated from the surface of the base material and baked to form a metal film. Examples of the heat treatment method include laser light irradiation, microwave irradiation, infrared irradiation, or light irradiation by light baking. Laser light irradiation or light baking capable of locally heat-treating the ink layer is preferable. Note that the heat treatment can be performed in an air atmosphere, an inert gas atmosphere, or the like, but is preferably performed in an air atmosphere.
マイクロ波照射は、２．２〜２．８ＧＨｚの周波数と、０．００５〜２０Ｗ／ｃｍ３の照射強度で、３００〜５００℃の温度を保持するように、１〜６０秒間、有機溶媒を除去したインク層に施すことが好ましい。 Microwave irradiation removes organic solvent for 1 to 60 seconds so as to maintain a temperature of 300 to 500 ° C. at a frequency of 2.2 to 2.8 GHz and an irradiation intensity of 0.005 to 20 W / cm 3. The ink layer is preferably applied.
赤外線照射は、赤外線のピーク波長を１．００〜２．２０μｍの範囲にして、３００〜５００℃の温度を保持するように、０．１〜３０秒間、有機溶媒を除去したインク層に施すことが好ましい。 Infrared irradiation is performed on the ink layer from which the organic solvent has been removed for 0.1 to 30 seconds so that the peak wavelength of infrared rays is in the range of 1.00 to 2.20 μm and the temperature of 300 to 500 ° C. is maintained. Is preferred.
レーザ光照射としては、赤外線レーザ、ＹＡＧレーザが好ましい。また光焼成による光照射で使用される光源としては、水銀灯、メタルハライドランプ、キセノンランプ、ケミカルランプ、カーボンアーク灯等がある。放射線としては、電子線、Ｘ線、イオンビーム、遠赤外線等が挙げられる。また、ｇ線、ｉ線、Ｄｅｅｐ−ＵＶ光、高密度エネルギービーム（レーザビーム）も光源として使用される。これらの光照射の具体的な態様としては、赤外線レーザによる走査露光、キセノン放電灯などの高照度フラッシュ露光、赤外線ランプ露光などが好適に挙げられる。 As the laser beam irradiation, an infrared laser or a YAG laser is preferable. Examples of light sources used for light irradiation by light baking include mercury lamps, metal halide lamps, xenon lamps, chemical lamps, and carbon arc lamps. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Also, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used as the light source. Specific examples of such light irradiation include scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.
光照射は、フラッシュランプによる光照射が好ましく、フラッシュランプによるパルス光照射であることがより好ましい。高エネルギーのパルス光の照射は、インク層を形成した部分の表面を、極めて短い時間で集中して３００〜５００℃の温度を保持するように、加熱することができるため、基材への熱の影響を極めて小さくすることができる。 The light irradiation is preferably light irradiation with a flash lamp, and more preferably pulsed light irradiation with a flash lamp. Irradiation with high-energy pulsed light can heat the surface of the portion where the ink layer is formed so as to concentrate in an extremely short time and maintain a temperature of 300 to 500 ° C. Can be made extremely small.
パルス光の照射エネルギーとしては、１〜１００Ｊ／ｃｍ２が好ましく、１〜３０Ｊ／ｃｍ２がより好ましく、パルス幅としては１μ秒〜１００ｍ秒が好ましく、１０μ秒〜１０ｍ秒がより好ましい。パルス光の照射時間は、１〜１００ｍ秒が好ましく、１〜５０ｍ秒がより好ましく、１〜２０ｍ秒が更に好ましい。 The irradiation energy of the pulse light is preferably 1~100J / cm 2, more preferably 1~30J / cm 2, preferably 1μ seconds ~100m sec as a pulse width, and more preferably 10μ sec ~10m seconds. The irradiation time of the pulsed light is preferably 1 to 100 milliseconds, more preferably 1 to 50 milliseconds, and further preferably 1 to 20 milliseconds.
以上の方法により、金属の有機化合物である金インクを銅含有基材表面に塗布して金インク層を形成し、このインク層の有機溶媒を除去すると、有機金属塩の薄膜が形成される。この薄膜にレーザ光照射等の熱処理を加えると、薄膜に含有する有機物が酸化分解し、同時に金属イオンと銅含有基材表面の酸化膜が還元され、ポーラスでない緻密な皮膜が形成される。この結果、銅基材表面に密着性の高いメッキ膜として使用可能な金属膜が形成される。 When the gold ink which is a metal organic compound is apply | coated to the copper containing base-material surface by the above method, a gold ink layer is formed and the organic solvent of this ink layer is removed, the organic metal salt thin film will be formed. When a heat treatment such as laser beam irradiation is applied to the thin film, organic substances contained in the thin film are oxidatively decomposed, and at the same time, the oxide film on the surface of the metal ions and the copper-containing substrate is reduced to form a dense non-porous film. As a result, a metal film that can be used as a plating film with high adhesion is formed on the surface of the copper substrate.
次に本発明の実施例を比較例とともに詳しく説明する。 Next, examples of the present invention will be described in detail together with comparative examples.
＜実施例１＞
長さ１０ｍｍ、幅１０ｍｍ、厚さ０．５ｍｍの大きさを有し、ニッケルめっき厚が３μｍのニッケルめっき銅条（Ｃｕ９７質量％以上、Ｍｇ１．９質量％以下の銅条（三菱伸銅社製、製品名：ＭＳＰ５））を銅含有基板として用い、この基板の表面に金レジネートインク（大研化学社製：Ａｕ−２２０１Ｙ−１０）を幅０．５ｍｍ、長さ０．５ｍｍ、厚さ０．３μｍとなるようにスクリーン印刷法によりパターン印刷し、金レジネートインク層を形成した。次に、表面温度１００℃に加熱したホットプレート上に、この基板を１０分間置くことで、金レジネートインク層に含まれる有機溶媒を除去した。その後、光焼成装置（PulseForge PF1200）を用いて、上記基板の表面から、金レジネートインク層が形成された部分に照射エネルギー１Ｊ／ｃｍ２で４００℃の温度を保持するように、照射エネルギー１Ｊ／ｃｍ２で１０ｍ秒間パルス光を照射し続けることで、基板の表面に金属膜を形成した試験片を得た。
<Example 1>
A nickel-plated copper strip having a length of 10 mm, a width of 10 mm, and a thickness of 0.5 mm, and a nickel plating thickness of 3 μm (a copper strip of Cu 97 mass% or more and Mg 1.9 mass% or less (manufactured by Mitsubishi Shindoh Co., Ltd.) , Product name: MSP5)) as a copper-containing substrate, and a gold resinate ink (Daiken Chemical Co., Ltd .: Au-2201Y-10) is applied to the surface of this substrate with a width of 0.5 mm, a length of 0.5 mm, and a thickness of 0. A pattern was printed by a screen printing method so as to be 3 μm to form a gold resinate ink layer. Next, this substrate was placed on a hot plate heated to a surface temperature of 100 ° C. for 10 minutes to remove the organic solvent contained in the gold resinate ink layer. Thereafter, using a light baking apparatus (PulseForge PF1200), the irradiation energy of 1 J / cm is maintained from the surface of the substrate to the portion where the gold resinate ink layer is formed at a temperature of 400 ° C. at an irradiation energy of 1 J / cm 2. A test piece having a metal film formed on the surface of the substrate was obtained by continuing to irradiate pulse light at cm 2 for 10 msec.
＜実施例２＞
銅条として、三菱伸銅社製、製品名：ＭＮＥＸ１０（Ｚｎ１０質量％、Ｎｉ０．６質量％、Ｃｕ８８質量％％以上）を用いた。これ以外は、実施例１と同様にして基板の表面に金属膜を形成した試験片を得た。
<Example 2>
As a copper strip, product name: MNEX10 (Zn 10 mass%, Ni 0.6 mass%, Cu 88 mass% or more) manufactured by Mitsubishi Shindoh Co., Ltd. was used. Except for this, a test piece having a metal film formed on the surface of the substrate was obtained in the same manner as in Example 1.
＜実施例３＞
金レジネートインクとして、ネオデカン酸金のα−ターピネオール溶液（１０質量％−Ａｕ）に、金ナノメタルインク（アルバックマテリアル社製：Ａｕ１Ｔ）を、金 重量換算で１：１になるように加えたものを用いた。これ以外は、実施例１と同様にして基板の表面に金属膜を形成した試験片を得た。
<Example 3>
As a gold resinate ink, a gold neometalate α-terpineol solution (10% by mass—Au) and a gold nanometal ink (manufactured by ULVAC Material Co., Ltd .: Au1T) added to a gold weight conversion ratio of 1: 1. Using. Except for this, a test piece having a metal film formed on the surface of the substrate was obtained in the same manner as in Example 1.
＜実施例４＞
光焼成装置の代わりに、Ｎｄ：ＹＡＧレーザー（発振部：ＬＡＳＥＲ ＳＯＳ社製ＳＯＳ８９５６ＱＳＳ）を用い、４５０℃の温度を保持するように、１０ｍＪ／パルスで、１０パルス照射し続けた。これ以外は、実施例１と同様にして基板の表面に金属膜を形成した試験片を得た。
<Example 4>
An Nd: YAG laser (oscillator: SOS8956QSS manufactured by LASER SOS) was used in place of the light baking apparatus, and irradiation was continued for 10 pulses at 10 mJ / pulse so as to maintain a temperature of 450 ° C. Except for this, a test piece having a metal film formed on the surface of the substrate was obtained in the same manner as in Example 1.
＜実施例５＞
銅含有基板として、ニッケルめっきがない銅条（三菱伸銅社製ＭＳＰ５）を用いた。これ以外は、実施例１と同様にして基板の表面に金属膜を形成した試験片を得た。
<Example 5>
As the copper-containing substrate, a copper strip without nickel plating (MSP5 manufactured by Mitsubishi Shindoh Co., Ltd.) was used. Except for this, a test piece having a metal film formed on the surface of the substrate was obtained in the same manner as in Example 1.
＜実施例６＞
光焼成装置の代わりに、マイクロ波加熱装置（（四国計測工業社製μReactor）を用いた。このマイクロ波加熱装置により、３００℃の温度を保持するように、周波数が２．４５ＧＨｚ、照射強度が１０Ｗ／ｃｍ３のマイクロ波を照射し続け、２０秒間保持した。これ以外は、実施例１と同様にして基板の表面に金属膜を形成した試験片を得た。
<Example 6>
Instead of the light baking apparatus, a microwave heating apparatus ((μReactor manufactured by Shikoku Sangyo Kogyo Co., Ltd.) was used. With this microwave heating apparatus, the frequency was 2.45 GHz and the irradiation intensity was maintained so as to maintain a temperature of 300 ° C. The microwave was continuously irradiated with 10 W / cm 3 and held for 20 seconds, except that a test piece having a metal film formed on the surface of the substrate was obtained in the same manner as in Example 1.
＜実施例７＞
光焼成装置の代わりに、赤外線ゴールドイメージ炉（アルバック理工社製RHL-E25P）を用いた。赤外線ランプ加熱装置により、４００℃の温度を保持するように、ピーク波長１．５μｍのマイクロ波を照射し続け、２０秒間保持した。これ以外は、実施例１と同様にして基板の表面に金属膜を形成した試験片を得た。
<Example 7>
Instead of the light baking apparatus, an infrared gold image furnace (RHL-E25P manufactured by ULVAC-RIKO) was used. With an infrared lamp heating device, microwaves having a peak wavelength of 1.5 μm were continuously irradiated so as to maintain a temperature of 400 ° C., and held for 20 seconds. Except for this, a test piece having a metal film formed on the surface of the substrate was obtained in the same manner as in Example 1.
＜比較例１＞
銅含有基板として、Ｍｇ、Ｚｎ、Ｎｉをいずれも含まない銅条（三菱伸銅社製ＯＦＳ）を用いた。これ以外は、実施例１と同様にして基板の表面に金属膜を形成した試験片を得た。
<Comparative Example 1>
As the copper-containing substrate, a copper strip (OFS manufactured by Mitsubishi Shindoh Co., Ltd.) containing none of Mg, Zn, and Ni was used. Except for this, a test piece having a metal film formed on the surface of the substrate was obtained in the same manner as in Example 1.
＜比較例２＞
光焼成装置の代わりに、マップル炉（ヤマト化学製ＦＰ３００）内で、金レジネートインク層に含まれる有機溶媒を除去した基板を３５０℃１０分加熱した。これ以外は、実施例１と同様にして基板の表面に金属膜を形成した試験片を得た。
<Comparative example 2>
Instead of the light baking apparatus, the substrate from which the organic solvent contained in the gold resinate ink layer was removed was heated at 350 ° C. for 10 minutes in a mapple furnace (FP300 manufactured by Yamato Chemical). Except for this, a test piece having a metal film formed on the surface of the substrate was obtained in the same manner as in Example 1.
＜比較試験及び評価＞
実施例１〜７及び比較例１〜２で得られた試験片について、パターンを印刷した箇所から１ｍｍ外側を、１８０゜曲げ加工を施した。曲げ加工部分について、表面から光学顕微鏡で確認し、クラックが観察されない場合は「良好」とし、クラックが観察された場合は「不良」とした。また、曲げ加工を施した後で、目視で金属膜の剥離が確認されたものを「良好」とし、確認されなかったものを「不良」とした。これらの結果を表１に示す。
<Comparison test and evaluation>
About the test piece obtained in Examples 1-7 and Comparative Examples 1-2, the 180 degree bending process was given to the 1 mm outer side from the location which printed the pattern. About the bending process part, it confirmed with the optical microscope from the surface, and when the crack was not observed, it was set as "good", and when the crack was observed, it was set as "defective". Moreover, after bending, what was visually confirmed to be peeled off was regarded as “good”, and what was not confirmed was regarded as “bad”. These results are shown in Table 1.
表１から明らかなように、実施例１〜７は、曲げ加工に対する耐久性の評価結果はいずれも良好であったが、比較例１〜２は、いずれも不良であった。 As is clear from Table 1, Examples 1 to 7 were all good in evaluation results of durability against bending, but Comparative Examples 1 and 2 were all bad.
本発明の金属膜の形成方法は、民生用機器、産業用機器、自動車用機器を中心とする、金属膜を有する接点部分の信頼性を向上した銅合金製端子金具を形成する方法に利用することができる。 The metal film forming method of the present invention is used for a method of forming a copper alloy terminal fitting with improved reliability of a contact portion having a metal film, mainly in consumer equipment, industrial equipment, and automobile equipment. be able to.
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