JP5773145B2 - Copper-based material having a copper diffusion prevention layer - Google Patents
Copper-based material having a copper diffusion prevention layer Download PDFInfo
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- JP5773145B2 JP5773145B2 JP2011147224A JP2011147224A JP5773145B2 JP 5773145 B2 JP5773145 B2 JP 5773145B2 JP 2011147224 A JP2011147224 A JP 2011147224A JP 2011147224 A JP2011147224 A JP 2011147224A JP 5773145 B2 JP5773145 B2 JP 5773145B2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 54
- 229910052802 copper Inorganic materials 0.000 title claims description 45
- 239000010949 copper Substances 0.000 title claims description 45
- 239000000463 material Substances 0.000 title claims description 40
- 238000009792 diffusion process Methods 0.000 title claims description 20
- 230000002265 prevention Effects 0.000 title claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 62
- 229910052709 silver Inorganic materials 0.000 claims description 62
- 239000004332 silver Substances 0.000 claims description 62
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 229910052763 palladium Inorganic materials 0.000 claims description 16
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 15
- 239000002344 surface layer Substances 0.000 claims description 15
- 239000010410 layer Substances 0.000 claims description 14
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 3
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 claims 1
- 238000007747 plating Methods 0.000 description 112
- 238000000034 method Methods 0.000 description 59
- 229910045601 alloy Inorganic materials 0.000 description 19
- 239000000956 alloy Substances 0.000 description 19
- 229910018104 Ni-P Inorganic materials 0.000 description 15
- 229910018536 Ni—P Inorganic materials 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 238000009713 electroplating Methods 0.000 description 11
- 230000007423 decrease Effects 0.000 description 8
- 238000007772 electroless plating Methods 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 3
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 3
- 229940098221 silver cyanide Drugs 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、銅の拡散防止層を有する銅系材料に関する。 The present invention relates to a copper-based material having a copper diffusion prevention layer.
LED（発光ダイオード）を用いる照明装置は、エネルギー消費が低く、長寿命であり、発熱電球や蛍光灯に代わる光源として広く注目されている。 An illumination device using an LED (light emitting diode) has low energy consumption, has a long lifetime, and is widely attracting attention as a light source that replaces a heat-generating bulb and a fluorescent lamp.
LEDを発光素子とするパッケージ化されたLED照明ユニットでは、LED 素子から発光する光を効率よく反射するために、光沢度や反射率が高い銀やアルミニウムを蒸着させた反射部を設けられている（下記特許文献１参照）。また、反射部に銀めっきを施すことによって、青色、青緑色、緑色発等の吸収が抑制されて高い発光出力が得られることも報告されている（下記特許文献２参照）。 Packaged LED lighting units that use LEDs as light emitting elements are provided with a reflective part on which silver or aluminum with high glossiness and reflectivity is deposited in order to efficiently reflect the light emitted from the LED elements. (See Patent Document 1 below). It has also been reported that by applying silver plating to the reflective portion, absorption of blue, blue-green, green, etc. is suppressed, and a high light emission output can be obtained (see Patent Document 2 below).
一方、銀めっき皮膜の下地として、安価で放熱性が良好な銅又は銅合金を用いる場合には、銅原子が銀めっき皮膜の表面に拡散して経時的に反射率が低下するという問題点がある。特に、白色LED発光素子は、消費電力の内で可視光に変換されるのは数十％程度であり、その他は熱となり、しかも、他の光源と比べて小型のために空間的に狭い領域に熱が集中し易く、長期間使用時には熱拡散により反射率の低下が大きな問題となる。 On the other hand, when copper or copper alloy that is inexpensive and has good heat dissipation is used as the base of the silver plating film, there is a problem that the reflectance decreases with time due to diffusion of copper atoms on the surface of the silver plating film. is there. In particular, white LED light-emitting elements are converted into visible light within the power consumption of about several tens of percent, others are heat, and they are spatially narrow due to their small size compared to other light sources. The heat tends to concentrate on the surface, and when used for a long period of time, a decrease in reflectance becomes a serious problem due to thermal diffusion.
銀めっきされた反射部を有するLED照明ユニットにおいて、銀めっきの下地に含まれる成分が銀めっき皮膜に拡散することを防止する方法として、Pd、Rh等の貴金属からなる拡散防止層を形成することが報告されている（下記特許文献３参照）。しかしながら、この方法では、拡散防止層に含まれる貴金属成分自体が銀めっき皮膜に拡散して、反射率の低下を生じるという問題点がある。 In a LED lighting unit having a silver-plated reflecting portion, a diffusion prevention layer made of a noble metal such as Pd or Rh is formed as a method for preventing components contained in the base of silver plating from diffusing into the silver plating film. Has been reported (see Patent Document 3 below). However, this method has a problem in that the noble metal component itself contained in the diffusion preventing layer diffuses into the silver plating film, resulting in a decrease in reflectance.
その他、例えば、表面にPd膜、Au膜などが形成されたプリント配線板についても、回路材料の銅が表面に拡散すると、ハンダ付け性やワイヤーボンディング性に悪影響を与えるという問題点がある。 In addition, for example, a printed wiring board having a Pd film, an Au film, or the like formed on the surface has a problem in that if copper as a circuit material diffuses on the surface, solderability and wire bonding properties are adversely affected.
本発明は、上記した従来技術の現状に鑑みてなされたものであり、その主な目的は、LED照明ユニット等の銅又は銅合金を基材として銀皮膜等の表面層が形成された材料において、基材に含まれる銅原子が表面層に拡散することを効果的に防止できる方法を提供することである。 The present invention has been made in view of the current state of the prior art described above, and its main purpose is a material in which a surface layer such as a silver film is formed using copper or a copper alloy as a base material such as an LED lighting unit. An object of the present invention is to provide a method capable of effectively preventing copper atoms contained in a base material from diffusing into a surface layer.
本発明者は、上記した目的達成すべく鋭意研究を重ねてきた。その結果、銅又は銅合金からなる基材上にパラジウム皮膜又は銀皮膜を形成した後、ニッケル皮膜又はニッケル合金皮膜を形成することによって、下地に含まれる銅原子の表面層への拡散が抑制され、例えば、表面層として銀皮膜を形成してLED照明ユニットの反射部として利用する場合に、高い反射率を長期間維持することが可能となることを見出し、ここに本発明を完成するに至った。 The inventor has conducted extensive research to achieve the above-described object. As a result, after the palladium film or silver film is formed on the substrate made of copper or copper alloy, the nickel film or nickel alloy film is formed, thereby suppressing the diffusion of copper atoms contained in the base layer to the surface layer. For example, when a silver film is formed as a surface layer and used as a reflection part of an LED lighting unit, it has been found that a high reflectance can be maintained for a long period of time, and the present invention has been completed here. It was.
即ち、本発明は、下記の銅の拡散防止層を有する銅系材料、及びLED照明ユニットを提供するものである。
項１． 銅又は銅合金を基材とする材料において、該基材上に、パラジウム皮膜又は銀皮膜と、ニッケル皮膜又はニッケル合金皮膜とが順次積層された構造の拡散防止層が形成されていることを特徴とする、銅の拡散防止層を有する銅系材料。
項２． 表面層として銀皮膜を有する上記項１に記載の銅系材料。
項３． LED照明ユニットにおける反射部である上記項２に記載の銅系材料。
項４． 上記項３に記載の銅系材料からなる反射部と、LED発光素子を有するLED照明ユニット。
That is, the present invention provides a copper-based material having the following copper diffusion prevention layer and an LED lighting unit.
Item 1. In a material based on copper or copper alloy, a diffusion prevention layer having a structure in which a palladium film or a silver film and a nickel film or a nickel alloy film are sequentially laminated is formed on the substrate. A copper-based material having a copper diffusion prevention layer.
Item 2. Item 2. The copper-based material according to Item 1, wherein the surface layer has a silver film.
Item 3. Item 3. The copper-based material according to Item 2, which is a reflection part in the LED lighting unit.
Item 4. An LED lighting unit comprising a reflective portion made of the copper-based material according to Item 3 and an LED light emitting element.
以下、本発明の銅系材料について詳細に説明する。
本発明の銅系材料は、銅又は銅合金を基材とする材料において、該基材上に、パラジウム皮膜又は銀皮膜と、ニッケル皮膜又はニッケル合金皮膜とが順次積層された構造の拡散防止層が形成されたものである。
Hereinafter, the copper-based material of the present invention will be described in detail.
The copper-based material of the present invention is a diffusion prevention layer having a structure in which a palladium film or a silver film, and a nickel film or a nickel alloy film are sequentially laminated on the base material of copper or a copper alloy. Is formed.
本発明の銅系材料における基材は、銅又は銅合金である。銅合金の種類については特に限定はないが、銅含有率が60重量％程度以上の銅合金が好ましく、例えば、銅亜鉛合金、銅スズ合金、銅ニッケル合金、銅アルミ合金などを用いることができる。 The base material in the copper-based material of the present invention is copper or a copper alloy. The type of copper alloy is not particularly limited, but a copper alloy having a copper content of about 60% by weight or more is preferable. For example, a copper zinc alloy, a copper tin alloy, a copper nickel alloy, a copper aluminum alloy, or the like can be used. .
本発明の銅系材料は、該基材上にパラジウム皮膜又は銀皮膜が形成され、次いで、この上にニッケル皮膜又はニッケル合金皮膜が形成された積層構造の拡散防止層を有するものである。 The copper-based material of the present invention has a diffusion preventing layer having a laminated structure in which a palladium film or a silver film is formed on the substrate, and then a nickel film or a nickel alloy film is formed thereon.
該拡散防止層におけるパラジウム皮膜の形成方法については特に限定はなく、真空蒸着法、スパッタリング法等の気相法、電気めっき法、無電解めっき法、置換めっき法などの湿式めっき法等の各種の方法で形成できる。これらの方法の内で、特に、電気めっき法、無電解めっき法、置換めっき法などの湿式めっき法によれば、複雑な装置を要することなく、簡単な方法で目的とするパラジウム皮膜を形成することができる。特に、電気めっき法によれば、低コストで効率よくパラジウム皮膜を形成できる。また、置換めっき法では、めっき浴中に短時間浸漬処理するだけの簡単な処理によって銅素材上にパラジウム皮膜を形成することでき、これにより十分な効果を得ることができる。 The method for forming the palladium film in the diffusion preventing layer is not particularly limited, and various methods such as a vapor deposition method such as a vacuum deposition method and a sputtering method, an electroplating method, an electroless plating method, a wet plating method such as a displacement plating method, and the like. It can be formed by the method. Among these methods, in particular, according to a wet plating method such as an electroplating method, an electroless plating method, and a displacement plating method, a desired palladium film is formed by a simple method without requiring a complicated apparatus. be able to. In particular, according to the electroplating method, a palladium film can be formed efficiently at low cost. Further, in the displacement plating method, a palladium film can be formed on a copper material by a simple treatment that is simply immersed in a plating bath for a short time, thereby obtaining a sufficient effect.
パラジウム皮膜の厚さについては特に限定はなく、置換めっき法によって形成される非常に薄いＰｄ皮膜でも十分な効果が得られるが、通常、0.001〜5μｍ程度が好ましく、0.01〜1μｍ程度がより好ましい。 The thickness of the palladium film is not particularly limited, and even a very thin Pd film formed by a displacement plating method can provide a sufficient effect, but is usually preferably about 0.001 to 5 μm, more preferably about 0.01 to 1 μm.
また、銀皮膜の形成方法についても特に限定はなく、真空蒸着法、スパッタリング法等の気相法、電気めっき法、無電解めっき法等の湿式めっき法等の任意の方法で形成することができる。これらの方法の内で、特に、電気めっき法、無電解めっき法などの湿式めっき法によれば、複雑な装置を要することなく、簡単な方法で目的とする銀皮膜を形成することができる。電気めっき法で形成する場合には、シアン化銀めっき浴などを用いてストライクめっきを行ってもよく、或いは、公知の光沢銀めっき皮膜、無光沢銀めっき皮膜等を形成してもよい。これらの銀めっき皮膜を形成するための銀めっき浴についても、公知のめっき浴を適宜用いることができる。銀皮膜の厚さについても特に限定はないが、通常は、0.01μm程度以上の膜厚とすることによって、十分な効果を得ることができ、経済性等を考慮すれば、0.01〜0.5μｍ程度とすればよい。 Also, the method for forming the silver film is not particularly limited, and it can be formed by any method such as a vapor deposition method such as a vacuum deposition method or a sputtering method, a wet plating method such as an electroplating method or an electroless plating method. . Among these methods, in particular, according to a wet plating method such as an electroplating method or an electroless plating method, a target silver film can be formed by a simple method without requiring a complicated apparatus. When forming by electroplating, strike plating may be performed using a silver cyanide plating bath or the like, or a known bright silver plating film, matte silver plating film or the like may be formed. As for the silver plating bath for forming these silver plating films, known plating baths can be used as appropriate. There is no particular limitation on the thickness of the silver film, but usually a sufficient effect can be obtained by setting the film thickness to about 0.01 μm or more, and considering economics, etc., about 0.01 to 0.5 μm. And it is sufficient.
パラジウム皮膜又は銀皮膜上には、ニッケル皮膜又はニッケル合金皮膜を形成する。ニッケル皮膜及びニッケル合金皮膜を形成する方法については特に限定はなく、真空蒸着法、スパッタリング法等の気相法、電気めっき法、無電解めっき法等の湿式めっき法等の任意の方法を適用できる。この場合にも、電気めっき法、無電解めっき法などの湿式めっき法によれば、複雑な装置を要することなく、簡単な方法で目的とするニッケル皮膜又はニッケル合金皮膜を形成することができる
電気めっき法によってニッケル皮膜を形成する場合には、ニッケルめっき浴の種類についても限定はなく、スルファミン酸ニッケルめっき浴、ワット浴、光沢剤を添加したワット浴等公知の電気ニッケルめっき浴を利用できる。
A nickel film or a nickel alloy film is formed on the palladium film or the silver film. The method for forming the nickel film and the nickel alloy film is not particularly limited, and any method such as a vapor deposition method such as a vacuum deposition method and a sputtering method, a wet plating method such as an electroplating method and an electroless plating method can be applied. . Also in this case, according to a wet plating method such as an electroplating method or an electroless plating method, a target nickel film or nickel alloy film can be formed by a simple method without requiring a complicated apparatus. When the nickel film is formed by a plating method, the kind of the nickel plating bath is not limited, and a known electro nickel plating bath such as a nickel sulfamate plating bath, a watt bath, a watt bath to which a brightener is added can be used.
ニッケル合金めっき皮膜としては、例えば、Ni-P合金めっき皮膜、Ni-B合金めっき皮膜、Ni-W合金めっき皮膜、Ni-Mo合金めっき皮膜、Ni-W-P合金めっき皮膜、Ni-Mo-P合金めっき皮膜等を例示できる。これらのニッケル合金めっき皮膜におけるNi含有量については、特に限定的ではないが、例えば、Ni含有量が６０重量%程度以上のニッケル合金めっき皮膜を好適に用いることができる。 Examples of nickel alloy plating film include Ni-P alloy plating film, Ni-B alloy plating film, Ni-W alloy plating film, Ni-Mo alloy plating film, Ni-WP alloy plating film, Ni-Mo-P alloy A plating film etc. can be illustrated. The Ni content in these nickel alloy plating films is not particularly limited. For example, a nickel alloy plating film having a Ni content of about 60% by weight or more can be suitably used.
ニッケル合金めっき皮膜の内で好ましい皮膜としては、例えば、Ni-P合金めっき皮膜を挙げることができる。Ni-P合金めっき皮膜におけるリン含有量については、通常、1〜13重量％程度が好ましく、3〜10重量％程度がより好ましい。 A preferable example of the nickel alloy plating film includes a Ni-P alloy plating film. The phosphorus content in the Ni-P alloy plating film is usually preferably about 1 to 13% by weight, more preferably about 3 to 10% by weight.
Ni-P合金めっき皮膜の形成方法についても特に限定はなく、電気Ni-P合金めっき浴、無電解Ni-P合金めっき浴などの公知の各種のNi-P合金めっき浴を用いて、常法に従って、基材とする銅又は銅合金上にNi-P合金めっき皮膜を形成すればよい。 There is no particular limitation on the method for forming the Ni-P alloy plating film, and various conventional Ni-P alloy plating baths such as an electric Ni-P alloy plating bath and an electroless Ni-P alloy plating bath are used. Accordingly, a Ni—P alloy plating film may be formed on the copper or copper alloy used as the base material.
電気Ni-P合金めっき浴の組成及びめっき条件の一例としては下記の通りである。
（１）めっき浴組成
硫酸ニッケル 200〜400 g/L、
塩化ニッケル 30〜60 g/L、
ホウ酸 30〜50 g/L、
亜リン酸1〜10g/L
（２）めっき条件
ｐH 1.0 〜4.5、浴温 40 〜60 ℃、電流密度 1〜3 A/dm2
以上の条件で電気Ni-P合金めっきを行うことによって、リン含有率2〜10％程度の範囲のNi-P合金めっき皮膜を形成することができる。
An example of the composition and plating conditions of the electric Ni—P alloy plating bath is as follows.
(1) Plating bath composition Nickel sulfate 200-400 g / L,
Nickel chloride 30-60 g / L,
Boric acid 30-50 g / L,
Phosphorous acid 1-10g / L
(2) Plating conditions pH 1.0 to 4.5, bath temperature 40 to 60 ° C, current density 1 to 3 A / dm 2
By performing electric Ni—P alloy plating under the above conditions, a Ni—P alloy plating film having a phosphorus content in the range of about 2 to 10% can be formed.
また、無電解Ni-P合金めっき浴としては、次亜リン酸塩を還元剤として含む公知の無電解Ni-P合金めっき浴を用いることができる。 As the electroless Ni—P alloy plating bath, a known electroless Ni—P alloy plating bath containing hypophosphite as a reducing agent can be used.
これらの内で、特に、電気Ni-P合金めっき浴を用いることによって、効率良くNi-P合金めっき皮膜を形成することができる。 Among these, in particular, an Ni—P alloy plating film can be efficiently formed by using an electric Ni—P alloy plating bath.
ニッケル皮膜又はニッケル合金皮膜の厚さについては、特に限定的ではないが、通常、1〜10μｍ程度とすることが好ましく、2〜5μｍ程度とすることがより好ましい。 The thickness of the nickel film or nickel alloy film is not particularly limited, but is usually preferably about 1 to 10 μm, more preferably about 2 to 5 μm.
本発明の銅系材料では、表面層の種類については特に限定はなく、例えば、Ａｕ，Ｐｄ等の表面層を有するプリント配線板の銅系材料からなる回路部分において、基材とする銅又は銅合金に含まれる銅原子が表面層に拡散することを効果的に防止できる。 In the copper-based material of the present invention, the type of the surface layer is not particularly limited. For example, in a circuit portion made of a copper-based material of a printed wiring board having a surface layer such as Au or Pd, copper or copper as a base material It is possible to effectively prevent copper atoms contained in the alloy from diffusing into the surface layer.
特に、表面層として銀皮膜が形成された銅系材料については、銅原子が表面の銀皮膜に拡散して、銀皮膜の反射率が低下することをすることを抑制できる。例えば、表面層として銀皮膜が形成された銅系材料をLED照明ユニットの反射部とする場合には、LED発光素子と表面に銀皮膜が形成された反射部とを有するパッケージ化されたLED照明ユニットにおいて、反射部における銅原子の熱拡散が抑制されて反射率の低下が少なく、高い反射率を長期間維持することができる。 In particular, for a copper-based material having a silver film as a surface layer, copper atoms can be prevented from diffusing into the silver film on the surface and the reflectance of the silver film being lowered. For example, when a copper-based material with a silver film formed as a surface layer is used as a reflective part of an LED lighting unit, a packaged LED illumination having an LED light emitting element and a reflective part with a silver film formed on the surface In the unit, the thermal diffusion of copper atoms in the reflecting portion is suppressed, and the reflectance is hardly lowered, and a high reflectance can be maintained for a long time.
この場合、反射部の表面に形成する銀皮膜の種類については特に限定はなく、真空蒸着法、スパッタリング法等の気相法、電気めっき法、無電解めっき法等の湿式めっき法等の任意の方法で形成することができる。例えば、電気めっき法で形成する場合には、必要に応じて、シアン化銀めっき浴などを用いてストライクめっきを行った後、公知の銀めっき浴を用いて銀めっき皮膜を形成すればよい。また、銀めっき皮膜は光沢銀めっき皮膜、無光沢銀めっき皮膜のいずれであってもよい。 In this case, there is no particular limitation on the type of silver film to be formed on the surface of the reflective portion, and any arbitrary method such as a vapor deposition method such as a vacuum deposition method or a sputtering method, a wet plating method such as an electroplating method or an electroless plating method, etc. Can be formed by a method. For example, when forming by an electroplating method, after performing strike plating using a silver cyanide plating bath or the like, a silver plating film may be formed using a known silver plating bath, if necessary. The silver plating film may be either a bright silver plating film or a matte silver plating film.
表面層としての銀皮膜の厚さについても特に限定はないが、通常は、0.1 〜10μm程度とすればよい。 The thickness of the silver film as the surface layer is not particularly limited, but is usually about 0.1 to 10 μm.
上記した銅又は銅合金からなる基材上に、パラジウム皮膜又は銀皮膜と、ニッケル皮膜又はニッケル合金皮膜とを順次積層した構造の拡散防止層を有し、表面層として銀皮膜を有する銅系材料を反射部とするLED照明ユニットの一例の概略図を図１に示す。このLED照明ユニットでは、セラミックス、ガラス等の基板上に電極を介してLED発光素子が配置されており、LED発光素子の周辺に発光した光を有効に活用するために反射部が設けられている。 A copper-based material having a diffusion prevention layer having a structure in which a palladium film or a silver film and a nickel film or a nickel alloy film are sequentially laminated on the base material made of copper or copper alloy, and having a silver film as a surface layer FIG. 1 shows a schematic diagram of an example of an LED lighting unit having a reflecting portion. In this LED lighting unit, LED light-emitting elements are arranged on electrodes such as ceramics and glass via electrodes, and a reflecting part is provided to effectively use the light emitted around the LED light-emitting elements. .
本発明の銅の拡散防止層を有する銅系材料によれば、銅又は銅合金を基材とする材料について、基材に含まれる銅原子が表面層に拡散することを効果的に防止できる。特に、表面層として銀皮膜を形成した銅系材料を反射部として有するLED照明ユニットによれば、基材から銅原子の熱拡散が抑制されて反射率の低下が少なく、高い反射率を長期間維持することができる。 According to the copper-based material having the copper diffusion preventing layer of the present invention, it is possible to effectively prevent the copper atoms contained in the base material from diffusing into the surface layer for the material based on copper or a copper alloy. In particular, according to an LED lighting unit having a copper-based material with a silver film as a surface layer as a reflection part, thermal diffusion of copper atoms from the base material is suppressed, so that there is little decrease in reflectance, and high reflectance is maintained for a long time. Can be maintained.
以下、実施例を挙げて本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１
圧延銅板（大きさ50×50mm、厚さ0.3mm）を被めっき物として、下記表１に示す工程で電気めっき法により、半光沢Pdめっきを行い、次いで、ニッケルめっきを行った後、引き続き、銀めっきを行った。使用したニッケルめっき浴の組成を表２に示し、銀めっき浴の組成を表３及び表４に示す。Pdめっきとしては、めっき時間を変化させて、厚さ０．００６〜０．１１４μｍの範囲の半光沢Pdのめっき皮膜を形成し、銀めっきとしては、光沢浴又は無光沢浴を用いて、光沢銀めっき皮膜又は無光沢銀めっき皮膜を形成した。
Example 1
Using a rolled copper plate (size 50 x 50 mm, thickness 0.3 mm) as an object to be plated, semi-glossy Pd plating was performed by electroplating in the steps shown in Table 1 below, followed by nickel plating, Silver plating was performed. The composition of the nickel plating bath used is shown in Table 2, and the composition of the silver plating bath is shown in Table 3 and Table 4. For Pd plating, the plating time is changed to form a semi-glossy Pd plating film with a thickness in the range of 0.006 to 0.114 μm. For silver plating, a glossy bath or matte bath is used to make the gloss A silver plating film or a dull silver plating film was formed.
上記した方法で銀めっき皮膜を形成した各試料の内で、厚さ0.1μｍの半光沢Ｐｄめっき皮膜を形成した試料について、波長450nmの光の反射率を測定した後、空気中、１５０で１０００時間の熱処理を行い、その後波長450nmの光の反射率を測定した。また、比較として、半光沢Pdめっきを行うことなく、その他は実施例１と同様の方法で、光沢銀めっき皮膜又は無光沢銀めっき皮膜を形成した試料についても、同様の方法で反射率を測定した。結果を下記表５に示す。 Among the samples in which the silver plating film was formed by the above-described method, the reflectance of light having a wavelength of 450 nm was measured for the sample in which the semi-gloss Pd plating film having a thickness of 0.1 μm was formed, and then 1000 in the air at 150 After heat treatment for a time, the reflectance of light having a wavelength of 450 nm was measured. For comparison, the reflectance was also measured in the same manner for the sample on which the bright silver plating film or matte silver plating film was formed, except that the semi-gloss Pd plating was not performed and the other methods were the same as in Example 1. did. The results are shown in Table 5 below.
以上の結果から明らかなように、銀めっき皮膜の下地としてPdめっき皮膜及びニッケルめっき皮膜を形成した場合には、Pdめっき皮膜を形成することなく、ニッケルめっき皮膜のみを形成した場合と比較して、熱処理後の反射率の低下が大きく抑制されていることが明らかである。従って、銀めっき皮膜を形成した反射部を有するLED照明ユニットにおいて、銅又は銅合金上に、Pdめっき皮膜を形成し、ニッケルめっき皮膜を形成した後、銀めっき皮膜を形成することによって、基材からの銅原子の熱拡散が抑制されて、高い反射率を長時間維持できることが判る。 As is clear from the above results, when the Pd plating film and the nickel plating film were formed as the base of the silver plating film, the Pd plating film was not formed, compared with the case where only the nickel plating film was formed. It is clear that the decrease in reflectance after heat treatment is greatly suppressed. Therefore, in an LED lighting unit having a reflective part on which a silver plating film is formed, a Pd plating film is formed on copper or a copper alloy, a nickel plating film is formed, and then a silver plating film is formed. It can be seen that the thermal diffusion of copper atoms from is suppressed and a high reflectance can be maintained for a long time.
また、Pdめっき皮膜の膜厚を0〜0.114μｍの範囲で変化させた試料の内で、光沢銀めっき皮膜を形成した試料について、波長450nmの光の反射率を測定した後、空気中、３８０℃で５分間の熱処理を行い、その後波長450nmの光の反射率を測定した。結果を下記表６に示す。 Further, the reflectance of light having a wavelength of 450 nm was measured for a sample on which a bright silver plating film was formed among samples in which the film thickness of the Pd plating film was changed in the range of 0 to 0.114 μm. A heat treatment was carried out at 5 ° C. for 5 minutes, and then the reflectance of light having a wavelength of 450 nm was measured. The results are shown in Table 6 below.
以上の結果から明らかなように、Ｐｄめっき皮膜を形成していない場合と比較すると、0.006μｍ以上のＰｄめっき皮膜を形成した場合に、熱処理後の反射率の低下が大きく抑制されていることが明らかである。 As is clear from the above results, when the Pd plating film of 0.006 μm or more is formed, the decrease in the reflectance after the heat treatment is greatly suppressed as compared with the case where the Pd plating film is not formed. it is obvious.
実施例２
実施例１の表１に記載された処理工程において、半光沢Ｐｄめっきに代えて、塩化パラジウム（PdCl2）の塩酸溶液（Pd濃度100ppm）に30℃、10秒間銅素材を浸漬することによって、置換Ｐｄめっき処理を行い、その後、表１に記載された工程に従って光沢銀めっき皮膜を形成した。
Example 2
In the treatment process described in Table 1 of Example 1, instead of semi-glossy Pd plating, a copper material was immersed in a hydrochloric acid solution (Pd concentration 100 ppm) of palladium chloride (PdCl 2 ) at 30 ° C. for 10 seconds. Substitution Pd plating treatment was performed, and then a bright silver plating film was formed according to the steps described in Table 1.
この試料について、波長450nmの光の反射率を測定した後、空気中、３８０℃で５分間の熱処理を行い、その後波長450nmの光の反射率を測定した。その結果、熱処理前の反射率が87.1%であったものが、熱処理後には88.6%となった。尚、熱処理後の反射率の上昇は、熱処理によってＡｇめっき皮膜の再結晶が生じたことによるものと思われる。 After measuring the reflectance of light with a wavelength of 450 nm, the sample was heat-treated in air at 380 ° C. for 5 minutes, and then the reflectance of light with a wavelength of 450 nm was measured. As a result, the reflectance before heat treatment was 87.1%, but after heat treatment was 88.6%. The increase in reflectance after the heat treatment seems to be due to the recrystallization of the Ag plating film caused by the heat treatment.
一方、置換Ｐｄめっき処理を行うことなく、それ以外は、上記方法と同様にして光沢銀めっき皮膜を形成した試料について、熱処理前後の波長450nmの光の反射率を測定した。その結果、熱処理前の反射率が８８％であったものが、熱処理後には５０％まで低下した。 On the other hand, the reflectance of light having a wavelength of 450 nm before and after the heat treatment was measured for the sample on which the bright silver plating film was formed in the same manner as the above method, except that the substitution Pd plating treatment was not performed. As a result, the reflectance before the heat treatment was 88%, but decreased to 50% after the heat treatment.
以上の結果から、置換めっき法によってＰｄめっき皮膜を形成した場合にも、熱処理後の反射率の低下を大きく抑制できることが判る。 From the above results, it can be seen that even when the Pd plating film is formed by the displacement plating method, the decrease in the reflectance after the heat treatment can be largely suppressed.
実施例３
実施例１の表１に記載された処理工程において、半光沢Ｐｄめっきに代えて、シアン化銀2g/Lとシアン化カリウム100g/Lを含むストライク銀めっき浴を用いて、浴温２５℃、電流密度１A/dm2で銀めっき皮膜を形成した。この際、銀めっきの時間は０〜３０秒の範囲で変化させた。その後、表１に記載された工程に従って光沢銀めっき皮膜を形成した。
Example 3
In the processing steps described in Table 1 of Example 1, instead of semi-gloss Pd plating, a strike silver plating bath containing 2 g / L of silver cyanide and 100 g / L of potassium cyanide was used, the bath temperature was 25 ° C., and the current density was A silver plating film was formed at 1 A / dm 2 . At this time, the silver plating time was changed in the range of 0 to 30 seconds. Thereafter, a bright silver plating film was formed according to the steps described in Table 1.
これらの試料について、波長450nmの光の反射率を測定した後、空気中、３８０℃で５分間の熱処理を行い、その後波長450nmの光の反射率を測定した。スルファミン酸ニッケルめっきの下地として形成した銀めっき皮膜のめっき時間及び膜厚と、熱処理前後の波長450nmの光の反射率との関係を下記表７に示す。尚、Agめっきの膜厚は、電流効率１００％として算出した値である。 After measuring the reflectance of light with a wavelength of 450 nm for these samples, heat treatment was performed in air at 380 ° C. for 5 minutes, and then the reflectance of light with a wavelength of 450 nm was measured. Table 7 below shows the relationship between the plating time and film thickness of the silver plating film formed as the base of the nickel sulfamate plating and the reflectance of light having a wavelength of 450 nm before and after the heat treatment. In addition, the film thickness of Ag plating is a value calculated as current efficiency of 100%.
以上の結果から明らかなように、スルファミン酸ニッケルめっきの下地として銀めっきを形成した場合には、銀めっきを形成していない場合と比較すると、熱処理後の反射率の低下が大きく抑制されていることが明らかである。
As is clear from the above results, when silver plating is formed as a base for nickel sulfamate plating, a decrease in reflectance after heat treatment is greatly suppressed as compared to the case where silver plating is not formed. It is clear.
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