JP5346965B2 - Silver plating material and method for producing the same - Google Patents
Silver plating material and method for producing the same Download PDFInfo
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 188
- 239000004332 silver Substances 0.000 title claims abstract description 188
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 187
- 238000007747 plating Methods 0.000 title claims abstract description 185
- 239000000463 material Substances 0.000 title claims abstract description 87
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 53
- VDMJCVUEUHKGOY-JXMROGBWSA-N (1e)-4-fluoro-n-hydroxybenzenecarboximidoyl chloride Chemical compound O\N=C(\Cl)C1=CC=C(F)C=C1 VDMJCVUEUHKGOY-JXMROGBWSA-N 0.000 claims abstract description 18
- 238000009713 electroplating Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 26
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 239000010935 stainless steel Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- QORAAKXXLPYSCF-UHFFFAOYSA-N [K+].[C-]#N.[C-]#N Chemical compound [K+].[C-]#N.[C-]#N QORAAKXXLPYSCF-UHFFFAOYSA-N 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 abstract description 46
- 230000007797 corrosion Effects 0.000 abstract description 46
- 239000002994 raw material Substances 0.000 abstract description 6
- HKSGQTYSSZOJOA-UHFFFAOYSA-N potassium argentocyanide Chemical compound [K+].[Ag+].N#[C-].N#[C-] HKSGQTYSSZOJOA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 4
- 238000000576 coating method Methods 0.000 abstract 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract 1
- ZLMJMSJWJFRBEC-OUBTZVSYSA-N potassium-40 Chemical compound [40K] ZLMJMSJWJFRBEC-OUBTZVSYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 17
- 238000004364 calculation method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- ISDDBQLTUUCGCZ-UHFFFAOYSA-N dipotassium dicyanide Chemical compound [K+].[K+].N#[C-].N#[C-] ISDDBQLTUUCGCZ-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-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
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Electroplating And Plating Baths Therefor (AREA)
- Manufacture Of Switches (AREA)
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Abstract
Description
本発明は、銀めっき材およびその製造方法に関し、特に、車載用や民生用の電気配線に使用されるコネクタ、スイッチ、リレーなどの接点や端子部品の材料として使用される銀めっき材およびその製造方法に関する。 The present invention relates to a silver plating material and a method for manufacturing the same, and in particular, a silver plating material used as a material for contacts and terminal parts such as connectors, switches, and relays used in electric wiring for vehicles and consumer use, and the manufacturing thereof. Regarding the method.
従来、コネクタやスイッチなどの接点や端子部品などの材料として、ステンレス鋼や銅または銅合金などの比較的安価で機械的特性に優れた素材に、電気特性や半田付け性などの必要に応じて、錫、銀、金などのめっきを施しためっき材が使用されている。 Conventionally, as materials for contacts and terminal parts such as connectors and switches, relatively inexpensive materials with excellent mechanical properties such as stainless steel, copper or copper alloys, as required for electrical characteristics and solderability A plating material plated with tin, silver, gold or the like is used.
しかし、従来の銀めっき材は、高湿環境下で使用する場合や、汗などの塩分を含む水分が付着した場合などに、素材またはその表面に形成された下地層と銀めっき皮膜との間の電池反応によって腐食する場合がある。このような電池反応は、例えば、めっき時に生じるピンホールの存在などによって、素材または下地層が部分的に露出することに起因している。 However, the conventional silver plating material is used between the material or the underlying layer formed on the surface and the silver plating film when used in a high humidity environment or when moisture containing salt such as sweat adheres. Corrosion may occur due to the battery reaction. Such a battery reaction is caused, for example, by partially exposing the material or the underlayer due to the presence of pinholes generated during plating.
このような腐食を防止する方法として、銀めっき皮膜を厚くする方法や、銀めっき皮膜の表面を有機皮膜で覆う方法(例えば、特許文献1参照)などが提案されている。 As a method for preventing such corrosion, a method of thickening the silver plating film, a method of covering the surface of the silver plating film with an organic film (for example, see Patent Document 1), and the like have been proposed.
しかし、銀めっき皮膜を厚くする方法ではコストが増大し、銀めっき皮膜の表面を有機皮膜で覆う方法では高温環境下における使用により有機皮膜が剥離される場合がある。 However, the method of increasing the thickness of the silver plating film increases the cost, and in the method of covering the surface of the silver plating film with the organic film, the organic film may be peeled off when used in a high temperature environment.
したがって、本発明は、このような従来の問題点に鑑み、銀めっき皮膜の厚さが薄く且つ銀めっき皮膜の表面を有機皮膜で覆わなくても、耐食性に優れた銀めっき材およびその製造方法を提供することを目的とする。 Therefore, in view of such conventional problems, the present invention provides a silver plating material excellent in corrosion resistance even if the thickness of the silver plating film is thin and the surface of the silver plating film is not covered with an organic film, and a method for producing the same. The purpose is to provide.
本発明者らは、上記課題を解決するために鋭意研究した結果、反射濃度が1.0以上であり且つ(111)面、(200)面、(220)面および(311)面のX線回折ピークの積分強度の合計に対する(111)面のX線回折ピークの積分強度の割合が40%以上である銀めっき皮膜を素材上に形成することにより、銀めっき皮膜の厚さが薄く且つ銀めっき皮膜の表面を有機皮膜で覆わなくても、耐食性に優れた銀めっき材を製造することができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that the reflection density is 1.0 or more and the (111) plane, (200) plane, (220) plane, and (311) plane X-rays. By forming on the material a silver plating film in which the ratio of the integrated intensity of the (111) plane X-ray diffraction peak to the total integrated intensity of the diffraction peaks is 40% or more, the silver plating film is thin and silver. It has been found that a silver plating material excellent in corrosion resistance can be produced without covering the surface of the plating film with an organic film, and the present invention has been completed.
すなわち、本発明による銀めっき材は、素材上に銀めっき皮膜が形成され、銀めっき皮膜の反射濃度が1.0以上であり、銀めっき皮膜の(111)面、(200)面、(220)面および(311)面のX線回折ピークの積分強度の合計に対する(111)面のX線回折ピークの積分強度の割合が40%以上であることを特徴とする。この銀めっき材において、反射濃度が1.2以上であり、(111)面のX線回折ピークの積分強度の割合が60%以上であるのが好ましい。また、素材がステンレス鋼からなり、素材と銀めっき皮膜との間にニッケルからなる下地層が形成されているのが好ましい。 That is, the silver plating material by this invention has a silver plating film formed on a raw material, the reflection density of a silver plating film is 1.0 or more, (111) plane of a silver plating film, (200) plane, (220 The ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane to the total integrated intensity of the X-ray diffraction peaks of the (3) plane and (311) plane is 40% or more. In this silver plating material, it is preferable that the reflection density is 1.2 or more, and the ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane is 60% or more. Moreover, it is preferable that a raw material consists of stainless steel and the base layer which consists of nickel is formed between the raw material and the silver plating film.
また、本発明による銀めっき材の製造方法は、5〜35mgのセレノシアン酸カリウムを含む銀めっき液を使用して、液温15〜30℃、電流密度3〜10A/dm2で電気めっきを行うことによって、素材上に銀めっき皮膜を形成することを特徴とする。この銀めっき材の製造方法において、銀めっき液が、80〜250g/Lのシアン化銀カリウムと40〜200g/Lのシアン化カリウムと3〜35mg/Lのセレノシアン酸カリウムとからなるのが好ましい。また、液温が15〜22℃であるのが好ましい。さらに、素材がステンレス鋼からなり、銀めっき皮膜を形成する前に、素材上にニッケルからなる下地層を形成するのが好ましい。 Moreover, the manufacturing method of the silver plating material by this invention performs electroplating by the liquid temperature of 15-30 degreeC, and the current density of 3-10 A / dm < 2 > using the silver plating liquid containing 5-35 mg potassium selenocyanate. Thus, a silver plating film is formed on the material. In this method for producing a silver plating material, the silver plating solution is preferably composed of 80 to 250 g / L of potassium cyanide, 40 to 200 g / L of potassium cyanide and 3 to 35 mg / L of potassium selenocyanate. Moreover, it is preferable that liquid temperature is 15-22 degreeC. Furthermore, it is preferable to form a base layer made of nickel on the material before the material is made of stainless steel and the silver plating film is formed.
本発明によれば、銀めっき皮膜の厚さが薄く且つ銀めっき皮膜の表面を有機皮膜で覆わなくても、耐食性に優れた銀めっき材を製造することができる。 ADVANTAGE OF THE INVENTION According to this invention, even if the thickness of a silver plating film is thin and it does not cover the surface of a silver plating film with an organic film, the silver plating material excellent in corrosion resistance can be manufactured.
本発明による銀めっき材の実施の形態では、ステンレス鋼などの素材上に銀めっき皮膜が形成され、銀めっき皮膜の反射濃度が1.0以上であり、銀めっき皮膜の(111)面、(200)面、(220)面および(311)面のX線回折ピークの積分強度の合計に対する(111)面のX線回折ピークの積分強度の割合が40%以上である。このような銀めっき材は、銀めっき皮膜の厚さが薄く且つ銀めっき皮膜の表面を有機皮膜で覆わなくても、優れた耐食性を有する。また、素材と銀めっき皮膜との間にニッケルからなる下地層が形成されているのが好ましい。 In the embodiment of the silver plating material according to the present invention, a silver plating film is formed on a material such as stainless steel, the reflection density of the silver plating film is 1.0 or more, the (111) surface of the silver plating film, ( The ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane to the total integrated intensity of the X-ray diffraction peaks of the (200) plane, (220) plane, and (311) plane is 40% or more. Such a silver plating material has excellent corrosion resistance even if the thickness of the silver plating film is thin and the surface of the silver plating film is not covered with an organic film. Moreover, it is preferable that the base layer which consists of nickel is formed between the raw material and the silver plating film.
特に、銀めっき皮膜の銀めっき皮膜の反射濃度が1.2以上であり、銀めっき皮膜の(111)面、(200)面、(220)面および(311)面のX線回折ピークの積分強度の合計に対する(111)面のX線回折ピークの積分強度の割合が60%以上であるのが好ましい。このような銀めっき材は、銀めっき皮膜の厚さが薄く且つ銀めっき皮膜の表面を有機皮膜で覆わなくても、極めて優れた耐食性を有する。 In particular, the reflection density of the silver plating film of the silver plating film is 1.2 or more, and the integration of the X-ray diffraction peaks of the (111), (200), (220) and (311) planes of the silver plating film. The ratio of the integrated intensity of the (111) plane X-ray diffraction peak to the total intensity is preferably 60% or more. Such a silver plating material has extremely excellent corrosion resistance even if the thickness of the silver plating film is thin and the surface of the silver plating film is not covered with an organic film.
なお、反射濃度は、反射率(=反射光量/入射光量)の常用対数である。また、銀結晶中の主要な結晶配向面は、(111)面、(200)面、(220)面および(311)面であり、本発明による銀めっき材の実施の形態では、これらの結晶面のX線回折ピークの積分強度の合計に対する(111)面のX線回折ピークの積分強度の占める割合を40%以上、好ましくは60%以上としている。 The reflection density is a common logarithm of reflectance (= reflected light amount / incident light amount). The main crystal orientation planes in the silver crystal are the (111) plane, the (200) plane, the (220) plane, and the (311) plane. In the embodiment of the silver plating material according to the present invention, these crystals The ratio of the integrated intensity of the (111) plane X-ray diffraction peak to the total integrated intensity of the X-ray diffraction peaks of the plane is 40% or more, preferably 60% or more.
上述した本発明による銀めっき材の実施の形態は、以下のような本発明による銀めっき材の製造方法の実施の形態によって製造することができる。 Embodiment of the silver plating material by this invention mentioned above can be manufactured by embodiment of the manufacturing method of the silver plating material by this invention as follows.
本発明による銀めっき材の製造方法の実施の形態では、80〜250g/Lのシアン化銀カリウムと40〜200g/Lのシアン化カリウムと3〜35mg/Lのセレノシアン酸カリウムとからなる銀めっき液を使用して、液温15〜30℃、電流密度3〜10A/dm2で電気めっきを行うことによって、ステンレス鋼などの素材(被めっき材)上に銀めっき皮膜を形成する。 In the embodiment of the method for producing a silver plating material according to the present invention, a silver plating solution comprising 80 to 250 g / L of potassium cyanide, 40 to 200 g / L of potassium cyanide and 3 to 35 mg / L of potassium selenocyanate is used. Using this, electroplating is performed at a liquid temperature of 15 to 30 ° C. and a current density of 3 to 10 A / dm 2 to form a silver plating film on a material (material to be plated) such as stainless steel.
特に、液温を15〜22℃にすれば、銀めっき皮膜の銀めっき皮膜の反射濃度が1.2以上、銀めっき皮膜の(111)面、(200)面、(220)面および(311)面のX線回折ピークの積分強度の合計に対する(111)面のX線回折ピークの積分強度の割合が60%以上であり、極めて優れた耐食性を有する銀めっき材を製造することができる。 In particular, when the liquid temperature is 15 to 22 ° C., the reflection density of the silver plating film is 1.2 or more, and the (111) plane, the (200) plane, the (220) plane, and the (311) of the silver plating film. The ratio of the integrated intensity of the (111) plane X-ray diffraction peak to the total integrated intensity of the X-ray diffraction peak of the () plane is 60% or more, and a silver plating material having extremely excellent corrosion resistance can be produced.
また、銀めっき皮膜を形成する前に、素材上にニッケルからなる下地層を形成するのが好ましい。なお、銀めっき皮膜を形成する電気めっきでは、被めっき材を陰極とし、銀電極板を陽極として、スターラにより400rpm程度で撹拌しながら行うのが好ましい。 Moreover, before forming a silver plating film, it is preferable to form the base layer which consists of nickel on a raw material. The electroplating for forming the silver plating film is preferably carried out while stirring at about 400 rpm with a stirrer using the material to be plated as the cathode and the silver electrode plate as the anode.
以下、本発明による銀めっき材およびその製造方法の実施例について詳細に説明する。 Examples of the silver plating material and the method for producing the same according to the present invention will be described in detail below.
[実施例1]
まず、被めっき材として70mm×50mm×0.054mmのSUS301金属基板を用意し、この被めっき材とSUS板をアルカリ脱脂液に入れ、被めっき材を陽極とし、SUS板を陰極として、電圧5Vで15秒間電解脱脂し、水洗した後、15%塩酸中で15秒間酸洗することによって前処理を行った。
[Example 1]
First, a 70 mm × 50 mm × 0.054 mm SUS301 metal substrate is prepared as a material to be plated, and the material to be plated and the SUS plate are placed in an alkaline degreasing solution, the material to be plated is used as an anode, the SUS plate is used as a cathode, and a voltage of 5V. The sample was subjected to electrolytic degreasing for 15 seconds, washed with water, and then pretreated by pickling in 15% hydrochloric acid for 15 seconds.
次に、150g/Lの塩化ニッケルと3質量%の塩酸とからなるニッケルストライクめっき液中において、前処理済みの被めっき材を陰極とし、ニッケル電極板を陽極として、スターラにより400rpmで撹拌しながら、電流密度2A/dm2で10秒間電気めっきを行うことにより、ニッケルストライクめっきを行った。 Next, in a nickel strike plating solution composed of 150 g / L of nickel chloride and 3% by mass of hydrochloric acid, the pretreated material to be plated is used as a cathode and the nickel electrode plate is used as an anode while stirring with a stirrer at 400 rpm. Nickel strike plating was performed by performing electroplating at a current density of 2 A / dm 2 for 10 seconds.
次に、350g/Lのスルファミン酸ニッケルと20g/Lの塩化ニッケルと35g/Lのホウ酸とからなるニッケルめっき液中において、ニッケルストライクめっき済みの被めっき材を陰極とし、SKニッケル電極板を陽極として、スターラにより400rpmで撹拌しながら、電流密度2A/dm2、液温50℃でニッケル膜厚が0.1μmになるまで電気めっきを行うことにより、ニッケルめっきを行った。 Next, in a nickel plating solution composed of 350 g / L nickel sulfamate, 20 g / L nickel chloride, and 35 g / L boric acid, a nickel strike plated material to be plated is used as a cathode, and an SK nickel electrode plate is formed. Nickel plating was performed by performing electroplating as an anode while stirring with a stirrer at 400 rpm until the nickel film thickness became 0.1 μm at a current density of 2 A / dm 2 and a liquid temperature of 50 ° C.
次に、3g/Lのシアン化銀カリウムと90g/Lのシアン化カリウムとからなる銀ストライクめっき液中において、ニッケルめっき済みの被めっき材を陰極とし、白金で被覆したチタン電極板を陽極として、スターラにより400rpmで撹拌しながら、電流密度2.5A/dm2で10秒間電気めっきを行うことにより、銀ストライクめっきを行った。 Next, in a silver strike plating solution composed of 3 g / L of potassium potassium cyanide and 90 g / L of potassium cyanide, a nickel plated plated material is used as a cathode, and a titanium electrode plate coated with platinum is used as an anode. The silver strike plating was performed by performing electroplating at a current density of 2.5 A / dm 2 for 10 seconds while stirring at 400 rpm.
次に、111g/Lのシアン化銀カリウムと120g/Lのシアン化カリウムと13mg/Lのセレノシアン酸カリウムからなるめっき液中において、銀ストライクめっき済みの被めっき材を陰極とし、銀電極板を陽極として、スターラにより400rpmで撹拌しながら、電流密度5A/dm2、液温18℃で銀膜厚が0.5μmになるまで電気めっきを行うことにより、銀めっきを行った。 Next, in a plating solution composed of 111 g / L of silver potassium cyanide, 120 g / L of potassium cyanide and 13 mg / L of potassium selenocyanate, the material subjected to silver strike plating is used as a cathode, and the silver electrode plate is used as an anode. While stirring with a stirrer at 400 rpm, silver plating was performed by performing electroplating until the silver film thickness became 0.5 μm at a current density of 5 A / dm 2 and a liquid temperature of 18 ° C.
このようにして作製した銀めっき材について、銀めっき皮膜の厚さおよび反射濃度の測定と、(111)面のX線回折ピークの積分強度の割合の算出と、耐食性の評価を行った。 The silver plating material thus produced was subjected to measurement of the thickness and reflection density of the silver plating film, calculation of the ratio of the integrated intensity of the (111) plane X-ray diffraction peak, and evaluation of corrosion resistance.
銀めっき皮膜の厚さは、蛍光X線膜厚計(エスアイアイ・ナノテクノロジー株式会社製のSFT9500)によって測定し、反射濃度は、濃度計(日本電色株式会社製のデンシトメーターND−1)を用いて、被めっき材の圧延方向に対して平行に測定した。その結果、銀めっき皮膜の厚さは0.495μmであり、反射濃度は1.41であった。 The thickness of the silver plating film was measured with a fluorescent X-ray film thickness meter (SFT9500, manufactured by SII Nano Technology Co., Ltd.), and the reflection density was measured using a densitometer (Nippon Denshoku Densitometer ND-1). ) Was measured in parallel with the rolling direction of the material to be plated. As a result, the thickness of the silver plating film was 0.495 μm and the reflection density was 1.41.
銀めっき皮膜の(111)面のX線回折ピークの積分強度の割合((111)配向比)は、X線回折(XRD)分析装置(理学電気株式会社製のRINT−3C)によって得られたX線回折パターンから、銀めっき皮膜の(111)面、(200)面、(220)面および(311)面のそれぞれのX線回折ピークの積分強度を求めた後、その積分強度の合計に対する(111)面のX線回折ピークの積分強度の割合(%)として算出した。その結果、銀めっき皮膜の(111)面のX線回折ピークの積分強度の割合は72%であった。 The ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane of the silver plating film ((111) orientation ratio) was obtained by an X-ray diffraction (XRD) analyzer (RINT-3C manufactured by Rigaku Corporation). From the X-ray diffraction pattern, the integrated intensity of each X-ray diffraction peak of the (111) plane, (200) plane, (220) plane and (311) plane of the silver plating film is obtained, and then the total integrated intensity is calculated. It was calculated as the ratio (%) of the integrated intensity of the X-ray diffraction peak of the (111) plane. As a result, the ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane of the silver plating film was 72%.
銀めっき皮膜の耐食性は、塩水噴霧試験機(スガ試験機製のCASSER−ISO−3)を用いて、試験液の塩化ナトリウム濃度50g/L、試験槽内温度35℃、空気飽和器の温度47℃の試験条件において24時間噴霧を行った後、JIS H8502のめっきの耐食性試験方法により、レイティングナンバ(以下「RN」という)標準図表を用いて評価した。RNは、腐食の度合いを目視で判断して0〜10の数字で表したものであり、数字が大きいほど腐食が小さい、すなわち耐食性が良好であることを示している。その結果、RNは10であり、全く腐食していなかったので、耐食性が極めて優れていることがわかった。 The corrosion resistance of the silver plating film was measured using a salt spray tester (CASSER-ISO-3 manufactured by Suga Test Instruments Co., Ltd.), the sodium chloride concentration of the test solution was 50 g / L, the temperature in the test tank was 35 ° C., and the temperature of the air saturator was 47 ° C. After spraying for 24 hours under the above test conditions, evaluation was performed using a rating number (hereinafter referred to as “RN”) standard chart according to the corrosion resistance test method for plating of JIS H8502. RN is a numerical value of 0 to 10 determined by visually judging the degree of corrosion. The larger the number, the smaller the corrosion, that is, the better the corrosion resistance. As a result, RN was 10, and it was found that the corrosion resistance was extremely excellent because it was not corroded at all.
[実施例2]
銀めっきにおいて、185g/Lのシアン化銀カリウムと90g/Lのシアン化カリウムと13mg/Lのセレノシアン酸カリウムとからなる銀めっき液を使用した以外は、実施例1と同様の方法により銀めっき材を作製した。
[Example 2]
In silver plating, a silver plating material was prepared in the same manner as in Example 1 except that a silver plating solution consisting of 185 g / L of potassium cyanide, 90 g / L of potassium cyanide and 13 mg / L of potassium selenocyanate was used. Produced.
このようにして作製した銀めっき材について、実施例1と同様の方法により、銀めっき皮膜の厚さおよび反射濃度の測定と、(111)面のX線回折ピークの積分強度の割合の算出と、耐食性の評価を行った。その結果、銀めっき皮膜の厚さは0.492μm、反射濃度は1.27、銀めっき皮膜の(111)面のX線回折ピークの積分強度の割合は66%、RNは10であり、耐食性が極めて優れていることがわかった。 For the silver plating material thus produced, the thickness and reflection density of the silver plating film and the calculation of the ratio of the integrated intensity of the X-ray diffraction peak on the (111) plane were performed in the same manner as in Example 1. The corrosion resistance was evaluated. As a result, the thickness of the silver plating film was 0.492 μm, the reflection density was 1.27, the ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane of the silver plating film was 66%, RN was 10, and the corrosion resistance Was found to be extremely good.
[実施例3]
銀めっきにおいて、111g/Lのシアン化銀カリウムと90g/Lのシアン化カリウムと13mg/Lのセレノシアン酸カリウムとからなる銀めっき液を使用し、液温を25℃とした以外は、実施例1と同様の方法により銀めっき材を作製した。
[Example 3]
In silver plating, Example 1 was used except that a silver plating solution consisting of 111 g / L of potassium cyanide cyanide, 90 g / L of potassium cyanide and 13 mg / L of potassium selenocyanate was used and the solution temperature was 25 ° C. A silver plating material was produced by the same method.
このようにして作製した銀めっき材について、実施例1と同様の方法により、銀めっき皮膜の厚さおよび反射濃度の測定と、(111)面のX線回折ピークの積分強度の割合の算出と、耐食性の評価を行った。その結果、銀めっき皮膜の厚さは0.503μm、反射濃度は1.07、銀めっき皮膜の(111)面のX線回折ピークの積分強度の割合は40%、RNは9.8−6であり、耐食性が優れていることがわかった。 For the silver plating material thus produced, the thickness and reflection density of the silver plating film and the calculation of the ratio of the integrated intensity of the X-ray diffraction peak on the (111) plane were performed in the same manner as in Example 1. The corrosion resistance was evaluated. As a result, the thickness of the silver plating film was 0.503 μm, the reflection density was 1.07, the ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane of the silver plating film was 40%, and RN was 9.8-6. It was found that the corrosion resistance was excellent.
[実施例4]
銀めっきにおいて、185g/Lのシアン化銀カリウムと120g/Lのシアン化カリウムと13mg/Lのセレノシアン酸カリウムとからなる銀めっき液を使用し、液温を25℃とした以外は、実施例1と同様の方法により銀めっき材を作製した。
[Example 4]
In silver plating, Example 1 was used except that a silver plating solution composed of 185 g / L of potassium cyanide, 120 g / L of potassium cyanide and 13 mg / L of potassium selenocyanate was used, and the solution temperature was 25 ° C. A silver plating material was produced by the same method.
このようにして作製した銀めっき材について、実施例1と同様の方法により、銀めっき皮膜の厚さおよび反射濃度の測定と、(111)面のX線回折ピークの積分強度の割合の算出と、耐食性の評価を行った。その結果、銀めっき皮膜の厚さは0.474μm、反射濃度は1.24、銀めっき皮膜の(111)面のX線回折ピークの積分強度の割合は56%、RNは9.8−6であり、耐食性が優れていることがわかった。 For the silver plating material thus produced, the thickness and reflection density of the silver plating film and the calculation of the ratio of the integrated intensity of the X-ray diffraction peak on the (111) plane were performed in the same manner as in Example 1. The corrosion resistance was evaluated. As a result, the thickness of the silver plating film was 0.474 μm, the reflection density was 1.24, the ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane of the silver plating film was 56%, and RN was 9.8-6. It was found that the corrosion resistance was excellent.
[比較例1]
銀めっきにおいて、111g/Lのシアン化銀カリウムと90g/Lのシアン化カリウムと52mg/Lのセレノシアン酸カリウムとからなる銀めっき液を使用した以外は、実施例1と同様の方法により銀めっき材を作製した。
[Comparative Example 1]
In silver plating, a silver plating material was prepared in the same manner as in Example 1 except that a silver plating solution composed of 111 g / L potassium potassium cyanide, 90 g / L potassium cyanide and 52 mg / L potassium selenocyanate was used. Produced.
このようにして作製した銀めっき材について、実施例1と同様の方法により、銀めっき皮膜の厚さおよび反射濃度の測定と、(111)面のX線回折ピークの積分強度の割合の算出と、耐食性の評価を行った。その結果、銀めっき皮膜の厚さは0.453μm、反射濃度は1.13、銀めっき皮膜の(111)面のX線回折ピークの積分強度の割合は35%、RNは8−4であり、耐食性が劣っていることがわかった。 For the silver plating material thus produced, the thickness and reflection density of the silver plating film and the calculation of the ratio of the integrated intensity of the X-ray diffraction peak on the (111) plane were performed in the same manner as in Example 1. The corrosion resistance was evaluated. As a result, the thickness of the silver plating film is 0.453 μm, the reflection density is 1.13, the ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane of the silver plating film is 35%, and the RN is 8-4. It was found that the corrosion resistance was inferior.
[比較例2]
銀めっきにおいて、185g/Lのシアン化銀カリウムと120g/Lのシアン化カリウムと13mg/Lのセレノシアン酸カリウムとからなる銀めっき液を使用し、電流密度を2A/dm2とした以外は、実施例1と同様の方法により銀めっき材を作製した。
[Comparative Example 2]
In Example of silver plating, except that a silver plating solution composed of 185 g / L of potassium cyanide, 120 g / L of potassium cyanide and 13 mg / L of potassium selenocyanate was used, and the current density was set to 2 A / dm 2. A silver plating material was produced by the same method as in No. 1.
このようにして作製した銀めっき材について、実施例1と同様の方法により、銀めっき皮膜の厚さおよび反射濃度の測定と、(111)面のX線回折ピークの積分強度の割合の算出と、耐食性の評価を行った。その結果、銀めっき皮膜の厚さは0.541μm、反射濃度は0.83、銀めっき皮膜の(111)面のX線回折ピークの積分強度の割合は49%、RNは2−2であり、耐食性が劣っていることがわかった。 For the silver plating material thus produced, the thickness and reflection density of the silver plating film and the calculation of the ratio of the integrated intensity of the X-ray diffraction peak on the (111) plane were performed in the same manner as in Example 1. The corrosion resistance was evaluated. As a result, the thickness of the silver plating film was 0.541 μm, the reflection density was 0.83, the ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane of the silver plating film was 49%, and RN was 2-2. It was found that the corrosion resistance was inferior.
[比較例3]
銀めっきにおいて、電流密度を2A/dm2、液温を25℃とした以外は、実施例1と同様の方法により銀めっき材を作製した。
[Comparative Example 3]
In silver plating, a silver plating material was produced in the same manner as in Example 1 except that the current density was 2 A / dm 2 and the liquid temperature was 25 ° C.
このようにして作製した銀めっき材について、実施例1と同様の方法により、銀めっき皮膜の厚さおよび反射濃度の測定と、(111)面のX線回折ピークの積分強度の割合の算出と、耐食性の評価を行った。その結果、銀めっき皮膜の厚さは0.503μm、反射濃度は0.37、銀めっき皮膜の(111)面のX線回折ピークの積分強度の割合は35%、RNは2−1であり、耐食性が劣っていることがわかった。 For the silver plating material thus produced, the thickness and reflection density of the silver plating film and the calculation of the ratio of the integrated intensity of the X-ray diffraction peak on the (111) plane were performed in the same manner as in Example 1. The corrosion resistance was evaluated. As a result, the thickness of the silver plating film is 0.503 μm, the reflection density is 0.37, the ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane of the silver plating film is 35%, and RN is 2-1. It was found that the corrosion resistance was inferior.
[比較例4]
銀めっきにおいて、185g/Lのシアン化銀カリウムと90g/Lのシアン化カリウムと13mg/Lのセレノシアン酸カリウムとからなる銀めっき液を使用し、電流密度を2A/dm2、液温を25℃とした以外は、実施例1と同様の方法により銀めっき材を作製した。
[Comparative Example 4]
In silver plating, a silver plating solution composed of 185 g / L of potassium cyanide, 90 g / L of potassium cyanide and 13 mg / L of potassium selenocyanate was used, the current density was 2 A / dm 2 , and the solution temperature was 25 ° C. A silver-plated material was produced by the same method as in Example 1 except that.
このようにして作製した銀めっき材について、実施例1と同様の方法により、銀めっき皮膜の厚さおよび反射濃度の測定と、(111)面のX線回折ピークの積分強度の割合の算出と、耐食性の評価を行った。その結果、銀めっき皮膜の厚さは0.471μm、反射濃度は0.29、銀めっき皮膜の(111)面のX線回折ピークの積分強度の割合は24%、RNは6−2であり、耐食性が劣っていることがわかった。 For the silver plating material thus produced, the thickness and reflection density of the silver plating film and the calculation of the ratio of the integrated intensity of the X-ray diffraction peak on the (111) plane were performed in the same manner as in Example 1. The corrosion resistance was evaluated. As a result, the thickness of the silver plating film was 0.471 μm, the reflection density was 0.29, the ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane of the silver plating film was 24%, and RN was 6-2. It was found that the corrosion resistance was inferior.
[比較例5]
銀めっきにおいて、111g/Lのシアン化銀カリウムと120g/Lのシアン化カリウムと52mg/Lのセレノシアン酸カリウムとからなる銀めっき液を使用し、電流密度を2A/dm2とした以外は、実施例1と同様の方法により銀めっき材を作製した。
[Comparative Example 5]
In Example of silver plating, except that a silver plating solution composed of 111 g / L potassium potassium cyanide, 120 g / L potassium cyanide and 52 mg / L potassium selenocyanate was used, and the current density was set to 2 A / dm 2. A silver plating material was produced by the same method as in No. 1.
このようにして作製した銀めっき材について、実施例1と同様の方法により、銀めっき皮膜の厚さおよび反射濃度の測定と、(111)面のX線回折ピークの積分強度の割合の算出と、耐食性の評価を行った。その結果、銀めっき皮膜の厚さは0.468μm、反射濃度は0.57、銀めっき皮膜の(111)面のX線回折ピークの積分強度の割合は23%、RNは8−4であり、耐食性が劣っていることがわかった。 For the silver plating material thus produced, the thickness and reflection density of the silver plating film and the calculation of the ratio of the integrated intensity of the X-ray diffraction peak on the (111) plane were performed in the same manner as in Example 1. The corrosion resistance was evaluated. As a result, the thickness of the silver plating film is 0.468 μm, the reflection density is 0.57, the ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane of the silver plating film is 23%, and the RN is 8-4. It was found that the corrosion resistance was inferior.
[比較例6]
銀めっきにおいて、111g/Lのシアン化銀カリウムと90g/Lのシアン化カリウムと52mg/Lのセレノシアン酸カリウムとからなる銀めっき液を使用し、電流密度を2A/dm2、液温を25℃とした以外は、実施例1と同様の方法により銀めっき材を作製した。
[Comparative Example 6]
In silver plating, a silver plating solution composed of 111 g / L of potassium cyanide cyanide, 90 g / L of potassium cyanide and 52 mg / L of potassium selenocyanate was used, the current density was 2 A / dm 2 , and the solution temperature was 25 ° C. A silver-plated material was produced by the same method as in Example 1 except that.
このようにして作製した銀めっき材について、実施例1と同様の方法により、銀めっき皮膜の厚さおよび反射濃度の測定と、(111)面のX線回折ピークの積分強度の割合の算出と、耐食性の評価を行った。その結果、銀めっき皮膜の厚さは0.491μm、反射濃度は0.16、銀めっき皮膜の(111)面のX線回折ピークの積分強度の割合は19%、RNは7−1であり、耐食性が劣っていることがわかった。 For the silver plating material thus produced, the thickness and reflection density of the silver plating film and the calculation of the ratio of the integrated intensity of the X-ray diffraction peak on the (111) plane were performed in the same manner as in Example 1. The corrosion resistance was evaluated. As a result, the thickness of the silver plating film is 0.491 μm, the reflection density is 0.16, the ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane of the silver plating film is 19%, and the RN is 7-1. It was found that the corrosion resistance was inferior.
[比較例7]
銀めっきにおいて、185g/Lのシアン化銀カリウムと120g/Lのシアン化カリウムと52mg/Lのセレノシアン酸カリウムとからなる銀めっき液を使用し、電流密度を2A/dm2、液温を25℃とした以外は、実施例1と同様の方法により銀めっき材を作製した。
[Comparative Example 7]
In silver plating, a silver plating solution composed of 185 g / L of potassium cyanide, 120 g / L of potassium cyanide and 52 mg / L of potassium selenocyanate was used, the current density was 2 A / dm 2 , and the solution temperature was 25 ° C. A silver-plated material was produced by the same method as in Example 1 except that.
このようにして作製した銀めっき材について、実施例1と同様の方法により、銀めっき皮膜の厚さおよび反射濃度の測定と、(111)面のX線回折ピークの積分強度の割合の算出と、耐食性の評価を行った。その結果、銀めっき皮膜の厚さは0.486μm、反射濃度は0.20、銀めっき皮膜の(111)面のX線回折ピークの積分強度の割合は18%、RNは7−3であり、耐食性が劣っていることがわかった。 For the silver plating material thus produced, the thickness and reflection density of the silver plating film and the calculation of the ratio of the integrated intensity of the X-ray diffraction peak on the (111) plane were performed in the same manner as in Example 1. The corrosion resistance was evaluated. As a result, the thickness of the silver plating film is 0.486 μm, the reflection density is 0.20, the ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane of the silver plating film is 18%, and the RN is 7-3. It was found that the corrosion resistance was inferior.
[比較例8]
銀めっきにおいて、111g/Lのシアン化銀カリウムと120g/Lのシアン化カリウムと52mg/Lのセレノシアン酸カリウムとからなる銀めっき液を使用し、液温を25℃とした以外は、実施例1と同様の方法により銀めっき材を作製した。
[Comparative Example 8]
In silver plating, Example 1 was used except that a silver plating solution composed of 111 g / L of potassium cyanide cyanide, 120 g / L of potassium cyanide and 52 mg / L of potassium selenocyanate was used, and the solution temperature was 25 ° C. A silver plating material was produced by the same method.
このようにして作製した銀めっき材について、実施例1と同様の方法により、銀めっき皮膜の厚さおよび反射濃度の測定と、(111)面のX線回折ピークの積分強度の割合の算出と、耐食性の評価を行った。その結果、銀めっき皮膜の厚さは0.451μm、反射濃度は0.86、銀めっき皮膜の(111)面のX線回折ピークの積分強度の割合は28%、RNは8−5であり、耐食性が劣っていることがわかった。 For the silver plating material thus produced, the thickness and reflection density of the silver plating film and the calculation of the ratio of the integrated intensity of the X-ray diffraction peak on the (111) plane were performed in the same manner as in Example 1. The corrosion resistance was evaluated. As a result, the thickness of the silver plating film is 0.451 μm, the reflection density is 0.86, the ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane of the silver plating film is 28%, and the RN is 8-5. It was found that the corrosion resistance was inferior.
[比較例9]
銀めっきにおいて、185g/Lのシアン化銀カリウムと90g/Lのシアン化カリウムと52mg/Lのセレノシアン酸カリウムとからなる銀めっき液を使用し、液温を25℃とした以外は、実施例1と同様の方法により銀めっき材を作製した。
[Comparative Example 9]
In silver plating, Example 1 was used except that a silver plating solution composed of 185 g / L of potassium cyanide cyanide, 90 g / L of potassium cyanide and 52 mg / L of potassium selenocyanate was used, and the solution temperature was 25 ° C. A silver plating material was produced by the same method.
このようにして作製した銀めっき材について、実施例1と同様の方法により、銀めっき皮膜の厚さおよび反射濃度の測定と、(111)面のX線回折ピークの積分強度の割合の算出と、耐食性の評価を行った。その結果、銀めっき皮膜の厚さは0.508μm、反射濃度は0.36、銀めっき皮膜の(111)面のX線回折ピークの積分強度の割合は21%、RNは5−3であり、耐食性が劣っていることがわかった。 For the silver plating material thus produced, the thickness and reflection density of the silver plating film and the calculation of the ratio of the integrated intensity of the X-ray diffraction peak on the (111) plane were performed in the same manner as in Example 1. The corrosion resistance was evaluated. As a result, the thickness of the silver plating film is 0.508 μm, the reflection density is 0.36, the ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane of the silver plating film is 21%, and RN is 5-3. It was found that the corrosion resistance was inferior.
[比較例10]
銀めっきにおいて、185g/Lのシアン化銀カリウムと120g/Lのシアン化カリウムとからなる銀めっき液を使用し、電流密度を2A/dm2、液温を25℃とした以外は、実施例1と同様の方法により銀めっき材を作製した。
[Comparative Example 10]
In silver plating, Example 1 was used except that a silver plating solution consisting of 185 g / L of potassium cyanide cyanide and 120 g / L of potassium cyanide was used, the current density was 2 A / dm 2 , and the solution temperature was 25 ° C. A silver plating material was produced by the same method.
このようにして作製した銀めっき材について、実施例1と同様の方法により、銀めっき皮膜の厚さおよび反射濃度の測定と、(111)面のX線回折ピークの積分強度の割合の算出と、耐食性の評価を行った。その結果、銀めっき皮膜の厚さは0.516μm、反射濃度は0.5、銀めっき皮膜の(111)面のX線回折ピークの積分強度の割合は71%、RNは2−1であり、耐食性が劣っていることがわかった。 For the silver plating material thus produced, the thickness and reflection density of the silver plating film and the calculation of the ratio of the integrated intensity of the X-ray diffraction peak on the (111) plane were performed in the same manner as in Example 1. The corrosion resistance was evaluated. As a result, the thickness of the silver plating film is 0.516 μm, the reflection density is 0.5, the ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane of the silver plating film is 71%, and the RN is 2-1. It was found that the corrosion resistance was inferior.
実施例および比較例の銀めっき材の作製条件および評価結果をそれぞれ表1および表2に示し、銀めっき皮膜の反射濃度および(111)面のX線回折ピークの積分強度の割合と耐食性の評価との関係を図1に示す。 The production conditions and evaluation results of the silver plating materials of Examples and Comparative Examples are shown in Table 1 and Table 2, respectively, and the reflection concentration of the silver plating film and the ratio of the integrated intensity of the (111) plane X-ray diffraction peak and the corrosion resistance are evaluated. FIG. 1 shows the relationship.
表2および図1からわかるように、銀めっき皮膜の反射濃度が1.0以上で(111)面のX線回折ピークの積分強度の割合が40%以上の実施例1〜4の銀めっき材は、銀めっき皮膜の厚さが0.5μm程度と薄くても、耐食性が優れている。特に、銀めっき皮膜の反射濃度が1.2以上で(111)面のX線回折ピークの積分強度の割合が60%以上の実施例3〜4の銀めっき材は、銀めっき皮膜の厚さが0.5μm程度と薄くても、耐食性が極めて優れている。 As can be seen from Table 2 and FIG. 1, the silver plating materials of Examples 1 to 4 in which the reflection density of the silver plating film is 1.0 or more and the ratio of the integrated intensity of the X-ray diffraction peak of the (111) plane is 40% or more. Has excellent corrosion resistance even when the thickness of the silver plating film is as thin as about 0.5 μm. Particularly, the silver plating materials of Examples 3 to 4 in which the reflection density of the silver plating film is 1.2 or more and the ratio of the integrated intensity of the (111) plane X-ray diffraction peak is 60% or more are the thickness of the silver plating film. Is extremely excellent in corrosion resistance even if it is as thin as about 0.5 μm.
表1からわかるように、実施例1〜4の銀めっき材は、80〜250g/Lのシアン化銀カリウムと40〜200g/Lのシアン化カリウムと3〜35mg/Lのセレノシアン酸カリウムとからなる銀めっき液を使用して、液温15〜30℃、電流密度3〜10A/dm2で電気めっきを行うことにより製造することができ、特に、実施例3〜4の銀めっき材は、液温15〜22℃で電気めっきを行うことにより製造することができる。 As can be seen from Table 1, the silver plating materials of Examples 1 to 4 are silver composed of 80 to 250 g / L of potassium cyanide, 40 to 200 g / L of potassium cyanide and 3 to 35 mg / L of potassium selenocyanate. Using a plating solution, it can be manufactured by performing electroplating at a liquid temperature of 15 to 30 ° C. and a current density of 3 to 10 A / dm 2. In particular, the silver plating materials of Examples 3 to 4 are It can manufacture by performing electroplating at 15-22 degreeC.
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