JP2011214066A - Glossy nickel plating material, electronic component comprising glossy nickel plating material, and process for production of glossy nickel plating material - Google Patents
Glossy nickel plating material, electronic component comprising glossy nickel plating material, and process for production of glossy nickel plating material Download PDFInfo
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- JP2011214066A JP2011214066A JP2010083223A JP2010083223A JP2011214066A JP 2011214066 A JP2011214066 A JP 2011214066A JP 2010083223 A JP2010083223 A JP 2010083223A JP 2010083223 A JP2010083223 A JP 2010083223A JP 2011214066 A JP2011214066 A JP 2011214066A
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- nickel plating
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 238000007747 plating Methods 0.000 title claims abstract description 96
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 title abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 6
- 239000010935 stainless steel Substances 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 19
- 238000005096 rolling process Methods 0.000 abstract description 6
- 238000005498 polishing Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 21
- 229910001369 Brass Inorganic materials 0.000 description 5
- 239000010951 brass Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910009038 Sn—P Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 2
- 229940081974 saccharin Drugs 0.000 description 2
- 235000019204 saccharin Nutrition 0.000 description 2
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017824 Cu—Fe—P Inorganic materials 0.000 description 1
- 229910017876 Cu—Ni—Si Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 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
- 239000006174 pH buffer Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/16—Acetylenic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/18—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Mechanical Engineering (AREA)
Abstract
Description
本発明は、光沢ニッケルめっき材、光沢ニッケルめっき材を用いた電子部品、及び、光沢ニッケルめっき材の製造方法に関する。 The present invention relates to a bright nickel plated material, an electronic component using the bright nickel plated material, and a method for producing the bright nickel plated material.
端子、コネクタ等の電子部品、或いは、金属装飾品等には、金属基材に光沢ニッケルめっきを施した材料が用いられている。光沢ニッケルめっきを製造する際の問題としては、めっき外観がめっき素材の表面特性に影響される点が挙げられる。例えば、黄銅（Ｃｕ−３０％Ｚｎ）条に光沢ニッケルめっきを施す場合、黄銅素材が焼き鈍し材であると、めっき後の外観に良好な光沢が見られず、曇った外観、或いは、光沢と曇りとが混在するような外観になることがある。また、りん青銅（Ｃｕ−８％Ｓｎ−Ｐ）条に光沢ニッケルめっきを施す場合にも同様の問題点が確認されている。 For electronic parts such as terminals and connectors, or metal ornaments, a material obtained by applying bright nickel plating to a metal substrate is used. A problem in producing bright nickel plating is that the appearance of the plating is affected by the surface characteristics of the plating material. For example, when applying bright nickel plating to brass (Cu-30% Zn) strips, if the brass material is an annealed material, the appearance after plating is not good gloss, and the appearance is cloudy or gloss and cloudy May be mixed. Similar problems have also been confirmed when bright nickel plating is applied to phosphor bronze (Cu-8% Sn-P) strips.
このような問題を解決するために、例えば、特許文献１には、めっき性に優れた銅合金の製造方法が開示されている。そして、これによれば、銅合金表面の加工変質層を薄くすることにより、特に銀めっき又は銅めっきを良好に形成できると記載されている。 In order to solve such a problem, for example, Patent Document 1 discloses a method for producing a copper alloy having excellent plating properties. And according to this, it is described that silver plating or copper plating can be particularly favorably formed by thinning the work-affected layer on the surface of the copper alloy.
しかしながら、上述の銅合金は、銀めっき又は銅めっきへは良好に適用できるが、光沢ニッケルめっきにおいて、良好な光沢を得ることは非常に難しく、未だ改善の余地がある。そこで、本発明は、良好な外観を有する光沢ニッケルめっき材、光沢ニッケルめっき材を用いた電子部品、及び、光沢ニッケルめっき材の製造方法を提供することを課題とする。 However, although the above-mentioned copper alloy can be satisfactorily applied to silver plating or copper plating, it is very difficult to obtain good gloss in bright nickel plating, and there is still room for improvement. Then, this invention makes it a subject to provide the manufacturing method of the bright nickel plating material which has a favorable external appearance, the electronic component using the bright nickel plating material, and a bright nickel plating material.
本発明者らは、鋭意検討の結果、めっき処理を行う金属基材の表面に加工変質層を形成することで、外観良好な光沢ニッケルめっきが得られるという、特許文献１とは相反する事実を見出した。 As a result of intensive studies, the inventors have found that the formation of a work-affected layer on the surface of a metal substrate to be plated provides a bright nickel plating with a good appearance, which is contrary to Patent Document 1. I found it.
以上の知見を基礎として完成した本発明は一側面において、表面の加工変質層の厚さが０．２μｍ以上である金属基材と、該金属基材の該表面に形成したニッケルめっき層とを備えた光沢ニッケルめっき材である。 The present invention completed on the basis of the above knowledge, in one aspect, comprises a metal base material having a thickness of 0.2 μm or more of a work-affected layer on the surface, and a nickel plating layer formed on the surface of the metal base material. A bright nickel plating material provided.
本発明に係る光沢ニッケルめっき材の更に別の一実施形態においては、加工変質層の厚さが０．２５〜３．０μｍである。 In still another embodiment of the bright nickel plating material according to the present invention, the thickness of the work-affected layer is 0.25 to 3.0 μm.
本発明に係る光沢ニッケルめっき材の更に別の一実施形態においては、加工変質層の厚さが０．３〜２．０μｍである。 In still another embodiment of the bright nickel plating material according to the present invention, the thickness of the work-affected layer is 0.3 to 2.0 μm.
本発明に係る光沢ニッケルめっき材の更に別の一実施形態においては、ニッケルめっき層を構成するニッケルの結晶粒径が０．３μｍ以下である。 In still another embodiment of the bright nickel plating material according to the present invention, the crystal grain size of nickel constituting the nickel plating layer is 0.3 μm or less.
本発明に係る光沢ニッケルめっき材の更に別の一実施形態においては、ニッケルめっき層を構成するニッケルの結晶粒径が０．０１〜０．３μｍである。 In still another embodiment of the bright nickel plating material according to the present invention, the crystal grain size of nickel constituting the nickel plating layer is 0.01 to 0.3 μm.
本発明に係る光沢ニッケルめっき材の更に別の一実施形態においては、金属基材が、ステンレス、銅、又は、銅合金で形成されている。 In still another embodiment of the bright nickel plating material according to the present invention, the metal substrate is formed of stainless steel, copper, or a copper alloy.
本発明は別の一側面において、本発明に係る光沢ニッケルめっき材を用いた電子部品である。 In another aspect, the present invention is an electronic component using the bright nickel plating material according to the present invention.
本発明は更に別の一側面において、表面の加工変質層の厚さが０．２μｍ以上である金属基材を準備し、該表面にニッケルめっき層を形成する光沢ニッケルめっき材の製造方法である。 In yet another aspect of the present invention, there is provided a method for producing a bright nickel-plated material, comprising preparing a metal base material having a surface-affected layer having a thickness of 0.2 μm or more and forming a nickel plating layer on the surface. .
本発明に係る光沢ニッケルめっき材の製造方法の一実施形態においては、ニッケルめっき層を構成するニッケルの結晶粒径が０．０１〜０．３μｍ以下である。 In one embodiment of the method for producing a bright nickel plating material according to the present invention, the crystal grain size of nickel constituting the nickel plating layer is 0.01 to 0.3 μm or less.
本発明によれば、良好な外観を有する光沢ニッケルめっき材、光沢ニッケルめっき材を用いた電子部品、及び、光沢ニッケルめっき材の製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the bright nickel plating material which has a favorable external appearance, the electronic component using the bright nickel plating material, and the manufacturing method of a bright nickel plating material can be provided.
（金属基材）
本発明に用いることのできる金属基材の形態に特に制限はないが、例えば、ステンレス鋼、銅、又は、銅合金が挙げられる。このうち、ステンレス鋼としては、マルテンサイト系、フェライト系、オーステナイト系等を用いることができる。また、銅又は銅合金は、コネクタや端子等の電子部品に使われる母材として公知である任意の銅又は銅合金としてよいが、電気・電子機器の接続端子等に用いられることを考慮すれば、電気伝導率の高いもの（例えば、ＩＡＣＳ（Ｉｎｔｅｒｎａｔｉｏｎａｌ Ａｎｎｅｉｌｄ Ｃｏｐｐｅｒ Ｓｔａｎｄｅｒｄ：国際標準軟銅の導電率を１００とした時の値）が１５〜８０％程度）を用いるのが好ましく、例えばＣｕ−Ｓｎ−Ｐ系（例えばりん青銅）、Ｃｕ−Ｚｎ系（例えば黄銅、丹銅）、Ｃｕ−Ｎｉ−Ｚｎ系（例えば洋白）、Ｃｕ−Ｎｉ−Ｓｉ系（コルソン合金）、Ｃｕ−Ｆｅ−Ｐ系合金などが挙げられる。また、金属基材の形状には特に制限はなく、板、条及びプレス品等の形態であってもよい。
(Metal base material)
Although there is no restriction | limiting in particular in the form of the metal base material which can be used for this invention, For example, stainless steel, copper, or a copper alloy is mentioned. Among these, as the stainless steel, martensite, ferrite, austenite, and the like can be used. Further, copper or copper alloy may be any copper or copper alloy known as a base material used for electronic parts such as connectors and terminals, but considering that it is used for connection terminals of electrical and electronic equipment. It is preferable to use a material having a high electrical conductivity (for example, IACS (International Anneal Copper Standard: a value when the conductivity of an international standard annealed copper is 100) is about 15 to 80%), for example, Cu-Sn-P. Type (for example, phosphor bronze), Cu-Zn type (for example, brass, red copper), Cu-Ni-Zn type (for example, white), Cu-Ni-Si type (Corson alloy), Cu-Fe-P type alloy, etc. Is mentioned. Moreover, there is no restriction | limiting in particular in the shape of a metal base material, Forms, such as a board, a strip, and a press product, may be sufficient.
ニッケルめっきを施す金属基材の表面には、加工変質層が０．２μｍ以上の厚さで存在する。加工変質層の厚さが０．２μｍ未満であると、当該表面に形成するニッケルめっき組織が全て、或いは部分的に粗大なものとなり、良好な外観のめっきが得られない。加工変質層とは、圧延加工やバフ研磨等によって金属表面に生じる結晶流の微細な層である。加工変質層の厚さは、好ましくは０．２５〜３．０μｍであり、より好ましくは０．３〜２．０μｍである。
一方、光沢ニッケルめっき材を製造する場合には、光沢剤を含有するめっきを用いて金属基材にめっき被膜を形成するが、上述のように金属基材表面の状態により、ニッケルめっきが光沢外観にならない場合がある。ニッケルめっきは下地の金属結晶の影響を受けやすいという特性を有するためである。例えば、金属基材の結晶粒が粗大であれば、めっきの結晶粒も大きくなり、結果としてめっき表面の凹凸が大きくなる。このため、曇った外観となる。一方、金属基材の結晶粒が微細であれば、めっき組織も微細となり、めっき表面は平滑になる。このため、めっきは光沢外観となる。
A work-affected layer is present at a thickness of 0.2 μm or more on the surface of the metal substrate to which nickel plating is applied. When the thickness of the work-affected layer is less than 0.2 μm, the nickel plating structure formed on the surface is entirely or partially coarse and plating with a good appearance cannot be obtained. The work-affected layer is a fine layer of crystal flow generated on the metal surface by rolling or buffing. The thickness of the work-affected layer is preferably 0.25 to 3.0 μm, more preferably 0.3 to 2.0 μm.
On the other hand, when manufacturing a bright nickel plating material, a plating film is formed on a metal substrate using plating containing a brightener, but the nickel plating has a glossy appearance depending on the state of the metal substrate surface as described above. It may not be. This is because nickel plating has a characteristic that it is easily influenced by the underlying metal crystal. For example, if the crystal grains of the metal substrate are coarse, the crystal grains of the plating also increase, and as a result, the unevenness of the plating surface increases. For this reason, it becomes a cloudy appearance. On the other hand, if the crystal grains of the metal substrate are fine, the plating structure becomes fine and the plating surface becomes smooth. For this reason, the plating has a glossy appearance.
（光沢ニッケルめっき材）
本発明に係る光沢ニッケルめっき材は、上述の金属基材の加工された表面に、ニッケルめっき層が形成されている。ニッケルめっき層は、金属基材の表面の金属の結晶粒径に対応する大きさの結晶粒径（０．３μｍ以下）を有するニッケルで構成されている。ニッケルめっき層は、このように結晶粒径が微細であるため、良好な光沢を有している。また、ニッケルめっき層を構成するニッケルの結晶粒径は、好ましくは０．０１〜０．３μｍである。
(Glossy nickel plating material)
In the bright nickel plating material according to the present invention, a nickel plating layer is formed on the processed surface of the above-described metal substrate. The nickel plating layer is made of nickel having a crystal grain size (0.3 μm or less) corresponding to the crystal grain size of the metal on the surface of the metal substrate. Since the nickel plating layer has such a fine crystal grain size, it has a good gloss. The crystal grain size of nickel constituting the nickel plating layer is preferably 0.01 to 0.3 μm.
ニッケルめっき層はニッケルで構成されるが、この中にはごく微量な有機光沢剤成分も含まれる。これは光沢剤成分がめっき工程で被膜に微量取り込まれるためである。
また、本発明に係る端子、コネクタ等の電子部品は、上述の光沢ニッケルめっき材を材料として構成されている。
The nickel plating layer is made of nickel, and this contains a very small amount of an organic brightener component. This is because a slight amount of the brightener component is taken into the film during the plating process.
In addition, electronic parts such as terminals and connectors according to the present invention are made of the above-described bright nickel plating material.
（光沢ニッケルめっき材の製造方法）
まず、ステンレス鋼、銅、又は、銅合金等で形成された金属基材を準備する。次に、例えば、圧延、スキンパス圧延、バフ研磨、ブラシ研磨によって金属基材の表面に加工変質層を形成する。加工変質層の厚さが０．２μｍ以上になるように加工の条件、例えば圧延加工度、バフ研磨時の圧力や時間を調整する。加工変質層の観察は、ＦＩＢ（Focused Ion Beam）による断面観察で行い、加工の成否を確認する。
(Manufacturing method of bright nickel plating material)
First, a metal substrate formed of stainless steel, copper, copper alloy or the like is prepared. Next, a work-affected layer is formed on the surface of the metal substrate by, for example, rolling, skin pass rolling, buffing, or brushing. The processing conditions such as the degree of rolling, the pressure during buffing and the time are adjusted so that the thickness of the work-affected layer is 0.2 μm or more. The processing-affected layer is observed by cross-sectional observation using FIB (Focused Ion Beam) to confirm the success or failure of the processing.
次に、光沢めっき浴を準備する。光沢めっき浴に用いる光沢めっき液は、水溶性ニッケル塩、ｐＨ緩衝剤、光沢剤を含有する。
ここで、水溶性ニッケル塩としては、例えば硫酸ニッケル、塩化ニッケル等が挙げられ、これらは合計２５０〜３５０ｇ／Ｌ添加される。
ｐＨ緩衝剤としては、例えば、ホウ酸、クエン酸等が挙げられ、これらは３５〜４５ｇ／Ｌ添加される。
光沢剤としては、例えば、サッカリン、１−４ブチンジオールが挙げられ、これらは０．１〜２ｇ／Ｌ添加される。
Next, a bright plating bath is prepared. The bright plating solution used for the bright plating bath contains a water-soluble nickel salt, a pH buffer, and a brightener.
Here, examples of the water-soluble nickel salt include nickel sulfate and nickel chloride, and these are added in a total amount of 250 to 350 g / L.
Examples of the pH buffering agent include boric acid and citric acid, and these are added in an amount of 35 to 45 g / L.
Examples of the brightener include saccharin and 1-4 butynediol, and these are added in an amount of 0.1 to 2 g / L.
光沢めっき液は水溶液であり、ｐＨ３〜５に調整することが好ましく、ｐＨ３．８〜４．２に調整することがより好ましい。
また、光沢めっき液は、浴温４０〜６０℃で使用するのが好ましく、４５〜５０℃で使用するのがより好ましい。
光沢めっき液のｐＨ及び浴温が上記範囲外の場合、めっき速度が遅かったり、外観不良を起し易い等の問題がある。
The bright plating solution is an aqueous solution, preferably adjusted to pH 3 to 5, and more preferably adjusted to pH 3.8 to 4.2.
The bright plating solution is preferably used at a bath temperature of 40 to 60 ° C., more preferably 45 to 50 ° C.
When the pH and bath temperature of the bright plating solution are out of the above ranges, there are problems such as a slow plating rate and a poor appearance.
続いて、上述の表面が加工された金属基材を光沢めっき浴内に所定時間浸漬し、所望の光沢を有する光沢ニッケルめっき基材を得る。この時、金属基材表面には結晶粒径が１μｍ以下、好ましくは０．０１〜０．２μｍ程度の加工変質層が形成されているため、該表面に形成されるめっき層の金属の結晶粒径もそれに対応して微細となる。このため、形成しためっき層の表面は平滑となり、良好な光沢を得ることができる。 Subsequently, the metal substrate having the surface processed as described above is immersed in a bright plating bath for a predetermined time to obtain a bright nickel-plated substrate having a desired gloss. At this time, since a work-affected layer having a crystal grain size of 1 μm or less, preferably about 0.01 to 0.2 μm is formed on the surface of the metal substrate, the metal crystal grains of the plating layer formed on the surface The diameter also becomes correspondingly fine. For this reason, the surface of the formed plating layer becomes smooth and good gloss can be obtained.
以下、本発明の実施例を示すが、これらは本発明をより良く理解するために提供するものであり、本発明が限定されることを意図するものではない。 EXAMPLES Examples of the present invention will be described below, but these are provided for better understanding of the present invention and are not intended to limit the present invention.
（例１：実施例１〜１０）
表１に示す厚さ０．６５ｍｍの金属基材を準備した。金属基材の表面には、バフ研磨により表１に示す厚さの加工変質層を形成した。この変質層の厚さは、ＦＩＢを用いて観察したものである。
また、金属基材の加工変質層を構成する金属の結晶粒径をＦＩＢにより観察した。
続いて、以下の組成の光沢めっき液を含有する光沢めっき浴を準備した。
・ＮｉＳＯ4・６Ｈ2Ｏ ２５０ｇ／ｌ
・ＮｉＣｌ2・６Ｈ2Ｏ ５０ｇ／ｌ
・ホウ酸 ４０サッカリン ２ｇ／ｌ
・１，４−ブチンジオール ０．２ｇ／ｌ
次に、表面を加工した金属基材を脱脂、酸洗した後、めっき浴に浸漬させ電流密度５Ａ/ｄｍ2でめっき層を形成した。光沢めっき浴は、ｐＨ４．０で４５℃とした。
図１に、実施例３に係る黄銅基材、加工変質層及びニッケルめっき層の拡大断面図を示す。
(Example 1: Examples 1 to 10)
A metal substrate having a thickness of 0.65 mm shown in Table 1 was prepared. On the surface of the metal substrate, a work-affected layer having a thickness shown in Table 1 was formed by buffing. The thickness of this deteriorated layer is observed using FIB.
Further, the crystal grain size of the metal constituting the work-affected layer of the metal substrate was observed by FIB.
Subsequently, a bright plating bath containing a bright plating solution having the following composition was prepared.
・ NiSO 4・ 6H 2 O 250g / l
・ NiCl 2・ 6H 2 O 50g / l
・ Boric acid 40 saccharin 2g / l
・ 1,4-Butynediol 0.2g / l
Then, degreased metal substrate obtained by processing the surface after pickling to form a plating layer at a current density of 5A / dm 2 is immersed in the plating bath. The bright plating bath was 45 ° C. at pH 4.0.
In FIG. 1, the expanded sectional view of the brass base material which concerns on Example 3, a work-affected layer, and a nickel plating layer is shown.
（例２：比較例１〜５）
比較例１〜５として、まず、実施例と同様の金属基材を準備した。次に、実施例と同様のめっき浴を準備して、これに該金属基材表面を加工しないで、あるいは軽くブラシ研磨する等の軽微な加工を行ってめっきした。めっき電流、及び浴温も実施例と同様に設定した。
(Example 2: Comparative Examples 1 to 5)
As Comparative Examples 1 to 5, first, the same metal substrate as in the Examples was prepared. Next, a plating bath similar to that of the example was prepared, and this was plated without performing processing on the surface of the metal substrate or by performing minor processing such as light brush polishing. The plating current and bath temperature were also set in the same manner as in the examples.
（評価）
ニッケルめっき層を構成するニッケルの結晶粒径をＦＩＢでの断面像により観察した。
ニッケルめっき層の光沢について外観観察を行った。外観評価は、光沢度計（日本電色工業製反射濃度計ＮＤ−１）を用いて行い、測定値が１．８超であるときを○とし、１．６〜１．８であるときを△とし、１．６未満であるときを×と評価した。
例１及び２の結果を表１に示す。
(Evaluation)
The crystal grain diameter of nickel constituting the nickel plating layer was observed by a cross-sectional image with FIB.
The appearance of the gloss of the nickel plating layer was observed. Appearance evaluation is performed using a gloss meter (Nippon Denshoku Co., Ltd. reflection densitometer ND-1), and when the measured value is over 1.8, the case is 1.6 to 1.8. It was set as Δ, and when it was less than 1.6, it was evaluated as ×.
The results of Examples 1 and 2 are shown in Table 1.
Claims (9)
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| JP2010083223A JP5869749B2 (en) | 2010-03-31 | 2010-03-31 | Manufacturing method of bright nickel plating material, and manufacturing method of electronic component using bright nickel plating material |
| KR1020147027348A KR20140121899A (en) | 2010-03-31 | 2011-03-03 | Glossy nickel plating material, electronic component comprising glossy nickel plating material, and process for production of glossy nickel plating material |
| KR1020157026833A KR20150115962A (en) | 2010-03-31 | 2011-03-03 | Glossy nickel plating material, electronic component comprising glossy nickel plating material, and process for production of glossy nickel plating material |
| KR1020127028203A KR20130027492A (en) | 2010-03-31 | 2011-03-03 | Glossy nickel plating material, electronic component comprising glossy nickel plating material, and process for production of glossy nickel plating material |
| PCT/JP2011/054954 WO2011122235A1 (en) | 2010-03-31 | 2011-03-03 | Glossy nickel plating material, electronic component comprising glossy nickel plating material, and process for production of glossy nickel plating material |
| CN201180016871.7A CN102812165B (en) | 2010-03-31 | 2011-03-03 | Gloss nickel plating material, the electronic component of use gloss nickel plating material and the preparation method of gloss nickel plating material |
| TW100109081A TWI431170B (en) | 2010-03-31 | 2011-03-17 | A glossy nickel plating material, an electronic component using a glossy nickel plating material, and a method of manufacturing a glossy nickel plating material |
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| KR (3) | KR20150115962A (en) |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014091845A (en) * | 2012-11-01 | 2014-05-19 | Dowa Metaltech Kk | Nickel plating material and method for manufacturing the same |
| JP2015017286A (en) * | 2013-07-09 | 2015-01-29 | 三菱伸銅株式会社 | Plating-fitted copper alloy sheet having excellent glossiness |
| CN105543921A (en) * | 2015-12-28 | 2016-05-04 | 上海运安制版有限公司 | Nickel plating non-grinding process for production of printing roller |
| JP2017059519A (en) * | 2015-09-18 | 2017-03-23 | アイシン精機株式会社 | Press-fit terminal |
| JP2018131643A (en) * | 2017-02-13 | 2018-08-23 | 新日鐵住金ステンレス株式会社 | Separator excellent in heat resistance for solid oxide type fuel cell and fuel cell using the same |
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| JP7190280B2 (en) * | 2018-08-10 | 2022-12-15 | 株式会社Lixil | plumbing fixtures |
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- 2011-03-03 WO PCT/JP2011/054954 patent/WO2011122235A1/en active Application Filing
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| JPS59133397A (en) * | 1983-01-20 | 1984-07-31 | Kasei Naoetsu:Kk | Formation of specular surface on extruded aluminum section by plating |
| JPS62107094A (en) * | 1985-11-06 | 1987-05-18 | Nippon Mining Co Ltd | Manufacture of nickel plated material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2014091845A (en) * | 2012-11-01 | 2014-05-19 | Dowa Metaltech Kk | Nickel plating material and method for manufacturing the same |
| JP2015017286A (en) * | 2013-07-09 | 2015-01-29 | 三菱伸銅株式会社 | Plating-fitted copper alloy sheet having excellent glossiness |
| JP2017059519A (en) * | 2015-09-18 | 2017-03-23 | アイシン精機株式会社 | Press-fit terminal |
| CN105543921A (en) * | 2015-12-28 | 2016-05-04 | 上海运安制版有限公司 | Nickel plating non-grinding process for production of printing roller |
| JP2018131643A (en) * | 2017-02-13 | 2018-08-23 | 新日鐵住金ステンレス株式会社 | Separator excellent in heat resistance for solid oxide type fuel cell and fuel cell using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201139757A (en) | 2011-11-16 |
| WO2011122235A1 (en) | 2011-10-06 |
| CN102812165B (en) | 2016-01-20 |
| TWI431170B (en) | 2014-03-21 |
| KR20140121899A (en) | 2014-10-16 |
| CN102812165A (en) | 2012-12-05 |
| KR20130027492A (en) | 2013-03-15 |
| KR20150115962A (en) | 2015-10-14 |
| JP5869749B2 (en) | 2016-02-24 |
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