JP2019044274A - Silver plated material and method for producing the same - Google Patents
Silver plated material and method for producing the same Download PDFInfo
- Publication number
- JP2019044274A JP2019044274A JP2018230536A JP2018230536A JP2019044274A JP 2019044274 A JP2019044274 A JP 2019044274A JP 2018230536 A JP2018230536 A JP 2018230536A JP 2018230536 A JP2018230536 A JP 2018230536A JP 2019044274 A JP2019044274 A JP 2019044274A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- plated product
- plated
- vickers hardness
- purity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 126
- 239000004332 silver Substances 0.000 title claims abstract description 126
- 239000000463 material Substances 0.000 title claims abstract description 108
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000007747 plating Methods 0.000 claims abstract description 114
- 238000000034 method Methods 0.000 claims abstract description 65
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 50
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000009713 electroplating Methods 0.000 claims abstract description 35
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 24
- 239000002344 surface layer Substances 0.000 claims abstract description 21
- 239000011669 selenium Substances 0.000 claims abstract description 19
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 5
- 238000012360 testing method Methods 0.000 claims description 85
- 239000000243 solution Substances 0.000 claims description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 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 description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- HKSGQTYSSZOJOA-UHFFFAOYSA-N potassium argentocyanide Chemical compound [K+].[Ag+].N#[C-].N#[C-] HKSGQTYSSZOJOA-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- MBBUQUXJJUSCJN-UHFFFAOYSA-N [K].[Ag]C#N Chemical compound [K].[Ag]C#N MBBUQUXJJUSCJN-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- KYEKHFSRAXRJBR-UHFFFAOYSA-M potassium;selenocyanate Chemical compound [K+].[Se-]C#N KYEKHFSRAXRJBR-UHFFFAOYSA-M 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 238000009429 electrical wiring Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- TXRHHNYLWVQULI-UHFFFAOYSA-L nickel(2+);disulfamate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O TXRHHNYLWVQULI-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 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
- 238000005406 washing Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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-plated material and a method of manufacturing the same, and in particular, a silver-plated material used as a material of contacts and terminals such as connectors, switches and relays used for electrical wiring for vehicles and consumer On the way.
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、銅または銅合金やステンレス鋼などの比較的安価で耐食性や機械的特性などに優れた素材に、電気特性や半田付け性などの必要な特性に応じて、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。 In the past, materials such as contacts and terminals such as connectors and switches need to be made of relatively inexpensive materials such as copper or copper alloy or stainless steel that are excellent in corrosion resistance and mechanical characteristics, such as electrical characteristics and solderability. Plating materials plated with tin, silver, gold, etc., are used according to their characteristics.
銅または銅合金やステンレス鋼などの素材に錫めっきを施した錫めっき材は、安価であるが、高温環境下における耐食性に劣っている。また、これらの素材に金めっきを施した金めっき材は、耐食性に優れ、信頼性が高いが、コストが高くなる。一方、これらの素材に銀めっきを施した銀めっき材は、金めっき材と比べて安価であり、錫めっき材と比べて耐食性に優れている。 Although tin plating material which tin-plated materials, such as copper or copper alloy and stainless steel, is cheap, it is inferior to corrosion resistance in a high temperature environment. Moreover, although the gold plating material which gave gold plating to these raw materials is excellent in corrosion resistance and has high reliability, cost becomes high. On the other hand, the silver plating material which silver-plated these materials is cheap compared with a gold plating material, and is excellent in corrosion resistance compared with a tin plating material.
また、コネクタやスイッチなどの接点や端子部品などの材料は、コネクタの挿抜やスイッチの摺動に伴う耐摩耗性も要求される。 In addition, materials such as contacts and terminal parts such as connectors and switches are also required to have wear resistance due to insertion and removal of connectors and sliding of switches.
しかし、銀めっき材では、再結晶により銀めっきの結晶粒径が増大し易く、この結晶粒径の増大により硬度が低くなって、耐摩耗性が低下するという問題がある（例えば、特許文献１参照）。 However, in the case of a silver-plated product, there is a problem that the crystal grain size of silver plating tends to increase due to recrystallization, and the hardness decreases due to the increase of this crystal grain size, resulting in a decrease in wear resistance (for example, Patent Document 1) reference).
このような銀めっき材の耐摩耗性を向上させるために、銀めっき中にアンチモンなどの元素を含有させることにより、銀めっき材の硬度を向上させる方法が知られている（例えば、特許文献２参照）。 In order to improve the wear resistance of such a silver plating material, there is known a method of improving the hardness of the silver plating material by containing an element such as antimony in the silver plating (for example, Patent Document 2) reference).
しかし、銀めっき中にアンチモンなどの元素を含有させると、銀が合金化して硬度が向上するものの、銀の純度が低くなるため、接触抵抗が増加するという問題がある。 However, when an element such as antimony is contained in the silver plating, although the silver is alloyed to improve the hardness, the purity of the silver is lowered, so that there is a problem that the contact resistance is increased.
したがって、本発明は、このような従来の問題点に鑑み、高い硬度を維持したまま、接触抵抗の増加を防止することができる、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。 Accordingly, in view of such conventional problems, it is an object of the present invention to provide a silver-plated product and a method of manufacturing the same, which can prevent an increase in contact resistance while maintaining high hardness.
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、８０〜１３０ｇ／Ｌの銀と、６０〜１３０ｇ／Ｌのシアン化カリウムと、３０〜８０ｍｇ／Ｌのセレンと、５０〜１９０ｇ／Ｌの炭酸カリウムとを含む銀めっき液中において、電気めっきを行って、素材上に銀からなる表層を形成することにより、高い硬度を維持したまま、接触抵抗の増加を防止することができる、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 80 to 130 g / L of silver, 60 to 130 g / L of potassium cyanide, 30 to 80 mg / L of selenium, and 50 to 190 g / L. In the silver plating solution containing potassium carbonate, electroplating is performed to form a surface layer made of silver on the material, thereby preventing an increase in contact resistance while maintaining high hardness. It has been found that a plating material can be produced, and the present invention has been completed.
すなわち、本発明による銀めっき材の製造方法は、８０〜１３０ｇ／Ｌの銀と、６０〜１３０ｇ／Ｌのシアン化カリウムと、３０〜８０ｍｇ／Ｌのセレンと、５０〜１９０ｇ／Ｌの炭酸カリウムとを含む銀めっき液中において、電気めっきを行うことによって、素材上に銀からなる表層を形成することを特徴とする。 That is, the method for producing a silver-plated product according to the present invention comprises 80 to 130 g / L of silver, 60 to 130 g / L of potassium cyanide, 30 to 80 mg / L of selenium, and 50 to 190 g / L of potassium carbonate In the silver plating solution containing it, it is characterized by forming the surface layer which consists of silver on a raw material by electroplating.
この銀めっき材の製造方法において、電気めっきが、電流密度３〜１２Ａ／ｄｍ２で行われるのが好ましい。また、銀めっき液が、シアン化銀カリウムと、シアン化カリウムと、セレノシアン酸カリウムと、炭酸カリウムとを含む水溶液からなるのが好ましい。さらに、素材が銅または銅合金からなるのが好ましく、素材と表層との間にニッケルからなる下地層を形成するのが好ましい。 In this method for producing a silver-plated product, electroplating is preferably performed at a current density of 3 to 12 A / dm 2 . The silver plating solution is preferably composed of an aqueous solution containing potassium cyanide, potassium cyanide, potassium selenocyanate and potassium carbonate. Furthermore, the material is preferably made of copper or a copper alloy, and it is preferable to form an underlayer made of nickel between the material and the surface layer.
また、本発明による銀めっき材は、上記の銀めっき材の製造方法によって製造され、反射濃度が０．３以上、表層のＡｇ純度が９９．９質量％以上であり、大気中において５０℃で１６８時間加熱する耐熱試験を行った後のビッカース硬さＨｖが１１０以上であることを特徴とする。この銀めっき材において、素材が銅または銅合金からなるのが好ましく、素材と表層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。 The silver plating material according to the present invention is manufactured by the above method for manufacturing a silver plating material, and has a reflection density of 0.3 or more, an Ag purity of the surface layer of 99.9 mass% or more, and at 50 ° C. in the air. It is characterized in that the Vickers hardness Hv after the heat resistance test of heating for 168 hours is 110 or more. In this silver-plated product, the material is preferably made of copper or a copper alloy, and it is preferable that a base layer made of nickel be formed between the material and the surface layer.
また、本発明による接点または端子部品は、上記の銀めっき材を材料として用いたことを特徴とする。 The contact or terminal part according to the present invention is characterized by using the above-mentioned silver-plated material as a material.
本発明によれば、高い硬度を維持したまま、接触抵抗の増加を防止することができる、銀めっき材およびその製造方法を提供することができる。 According to the present invention, it is possible to provide a silver-plated product and a method of manufacturing the same, which can prevent an increase in contact resistance while maintaining high hardness.
本発明による銀めっき材の製造方法の実施の形態では、８０〜１３０ｇ／Ｌ（好ましくは９０〜１２０ｇ／Ｌ）の銀と、６０〜１３０ｇ／Ｌ（好ましくは６５〜１２５ｇ／Ｌ）のシアン化カリウムと、３０〜８０ｍｇ／Ｌ（好ましくは３５〜７５ｍｇ／Ｌ）のセレンと、５０〜１９０ｇ／Ｌ（好ましくは７０〜１７０ｇ／Ｌ）の炭酸カリウムとを含む銀めっき液中において、電気めっきを行うことによって、素材上に銀からなる表層を形成する。このようにして銀めっき材を製造することにより、銀めっき材の高い硬度を維持したまま、接触抵抗の増加を防止することができる。 In the embodiment of the method for producing a silver-plated product according to the present invention, 80 to 130 g / L (preferably 90 to 120 g / L) of silver and 60 to 130 g / L (preferably 65 to 125 g / L) of potassium cyanide Electroplating in a silver plating solution containing 30 to 80 mg / L (preferably 35 to 75 mg / L) selenium and 50 to 190 g / L (preferably 70 to 170 g / L) potassium carbonate Form a surface layer made of silver on the material. By producing the silver-plated product in this manner, an increase in contact resistance can be prevented while maintaining the high hardness of the silver-plated product.
この銀めっき材の製造方法の実施の形態において、電気めっきが、液温１０〜５０℃（好ましくは２０〜４０℃）で行われるのが好ましく、電流密度３〜１２Ａ／ｄｍ２で行われるのが好ましい。また、銀めっき液が、シアン化銀カリウム（ＫＡｇ（ＣＮ）２）と、シアン化カリウム（ＫＣＮ）と、セレノシアン酸カリウム（ＫＳｅＣＮ）と、炭酸カリウム（Ｋ２ＣＯ３）とを含む水溶液からなるのが好ましい。 In the embodiment of the method for producing a silver-plated product, electroplating is preferably performed at a solution temperature of 10 to 50 ° C. (preferably 20 to 40 ° C.), and is performed at a current density of 3 to 12 A / dm 2 . Is preferred. In addition, the silver plating solution is an aqueous solution containing silver potassium cyanide (KAg (CN) 2 ), potassium cyanide (KCN), potassium selenocyanate (KSeCN), and potassium carbonate (K 2 CO 3 ). preferable.
また、銀めっき材のビッカース硬さＨｖが１１０以上であるのが好ましく、１２０以上であるのがさらに好ましい。また、銀めっき材を耐熱試験として５０℃で１６８時間加熱した後のビッカース硬さＨｖが１１０以上であるのが好ましく、１２０以上であるのがさらに好ましい。このようにビッカース硬さＨｖが１１０以上であれば、疵や打痕が付き難くなり、耐摩耗性に優れた銀めっき材になる。なお、耐熱試験前後のビッカース硬さＨｖは１６０程度以下でよい。 Further, the Vickers hardness Hv of the silver-plated product is preferably 110 or more, and more preferably 120 or more. Moreover, it is preferable that it is 110 or more, and, as for the Vickers hardness Hv after heating a silver plating material at 50 degreeC as a heat resistance test for 168 hours, it is more preferable that it is 120 or more. As described above, when the Vickers hardness Hv is 110 or more, it becomes difficult to form wrinkles and dents, and a silver-plated material having excellent wear resistance is obtained. The Vickers hardness Hv before and after the heat resistance test may be about 160 or less.
また、素材が銅または銅合金からなるのが好ましい。また、表層の厚さは、厚過ぎるとコストが高くなるだけでなく割れ易くなって銀めっき材の加工性が低下し、薄過ぎると銀めっき材の耐摩耗性が低下するため、２〜１０μｍであるのが好ましく、３〜７μｍであるのがさらに好ましく、４〜６μｍであるのが最も好ましい。 Moreover, it is preferable that a raw material consists of copper or a copper alloy. In addition, if the thickness of the surface layer is too thick, not only the cost increases but also it becomes easy to break and the workability of the silver-plated material is reduced, and when it is too thin, the wear resistance of the silver-plated material is reduced. Is preferred, 3 to 7 μm is more preferred, and 4 to 6 μm is most preferred.
また、素材と銀からなる表層との間の密着性を向上させるために、素材と表層との間にニッケルからなる下地層を形成するのが好ましい。この下地層の厚さは、薄過ぎると素材と銀からなる表層との間の密着性を向上させるには十分でなく、厚過ぎると銀めっき材の加工性が低下するため、０．３〜２．０μｍであるのが好ましく、０．５〜１．５μｍであるのがさらに好ましい。この下地層と銀からなる表層との間の密着性を向上させるために、下地層と表層との間に銀ストライクめっきよる中間層を形成してもよい。また、銀めっき材の接触抵抗は、１．０ｍΩ以下であるのが好ましく、０．７ｍΩ以下であるのがさらに好ましい。この銀めっき材の接触抵抗の増加を防止するために、表層のＡｇ純度が９９質量％以上であるのが好ましく、９９．５質量％以上であるのがさらに好ましい。 Further, in order to improve the adhesion between the material and the surface layer made of silver, it is preferable to form a base layer made of nickel between the material and the surface layer. If the thickness of the base layer is too thin, it is not sufficient to improve the adhesion between the material and the surface layer made of silver, and if it is too thick, the processability of the silver-plated product is lowered. The thickness is preferably 2.0 μm, and more preferably 0.5 to 1.5 μm. In order to improve the adhesion between the underlayer and the surface layer made of silver, an intermediate layer may be formed between the underlayer and the surface layer by silver strike plating. Further, the contact resistance of the silver-plated product is preferably 1.0 mΩ or less, and more preferably 0.7 mΩ or less. In order to prevent an increase in the contact resistance of the silver-plated product, the Ag purity of the surface layer is preferably 99% by mass or more, and more preferably 99.5% by mass or more.
上述した銀めっき材の製造方法の実施の形態により、素材上に銀からなる表層が形成された銀めっき材において、反射濃度が０．３以上（好ましくは１．０以上）、表層のＡｇ純度が９９．９質量％以上であり、大気中において５０℃で１６８時間加熱する耐熱試験を行った後のビッカース硬さＨｖが１１０以上である銀めっき材を製造することができる。なお、反射濃度が０．３未満であると、銀めっき材の外観が（鏡面から白色に変わり）無光沢化して、プレス加工時などに表面に疵が付き易くなる。 In the silver plating material in which the surface layer made of silver is formed on the material according to the embodiment of the method for manufacturing a silver plating material described above, the Ag concentration of the surface layer is 0.3 or more (preferably 1.0 or more) Is 99.9% by mass or more, and a silver-plated product having a Vickers hardness Hv of 110 or more after heat resistance test of heating at 50 ° C. for 168 hours in the atmosphere can be manufactured. When the reflection density is less than 0.3, the appearance of the silver-plated product becomes non-glossy (mirror surface changes to white), and the surface is easily wrinkled during press processing or the like.
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。 Hereinafter, examples of the silver-plated product and the method for producing the same according to the present invention will be described in detail.
［実施例１］
まず、素材（被めっき材）として６７ｍｍ×５０ｍｍ ×０．３ｍｍの純銅からなる圧延板を用意し、この被めっき材とＳＵＳ板をアルカリ脱脂液に入れ、被めっき材を陰極とし、ＳＵＳ板を陽極として、電圧５Ｖで３０秒間電解脱脂を行い、１５秒間水洗した後、３％硫酸中で１５秒間酸洗し、１５秒間水洗した。
Example 1
First, prepare a rolled plate consisting of pure copper of 67 mm x 50 mm x 0.3 mm as a material (material to be plated), put this material to be plated and a SUS plate in an alkaline degreasing solution, use the material to be plated as a cathode, As an anode, electrolytic degreasing was performed at a voltage of 5 V for 30 seconds, washed with water for 15 seconds, then pickled in 3% sulfuric acid for 15 seconds, and washed with water for 15 seconds.
次に、２５ｇ／Ｌの塩化ニッケルと３５ｇ／Ｌのホウ酸と５４０ｇ／Ｌのスルファミン酸ニッケル四水和物を含む水溶液からなる無光沢ニッケルめっき液中において、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５００ｒｐｍで撹拌しながら電流密度５Ａ／ｄｍ２で８５秒間電気めっき（無光沢ニッケルめっき）を行って、厚さ１μｍの無光沢ニッケルめっき皮膜を形成した後、１５秒間水洗した。 Next, in a non-bright nickel plating solution comprising an aqueous solution containing 25 g / L of nickel chloride, 35 g / L of boric acid, and 540 g / L of nickel sulfamate tetrahydrate, the material to be plated is used as a cathode and a nickel electrode Using a plate as an anode, electroplating (matte nickel plating) is performed for 85 seconds at a current density of 5 A / dm 2 while stirring with a stirrer at 500 rpm to form a 1 μm thick non-tacky nickel plating film, and then washing for 15 seconds did.
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を含む水溶液からなる銀ストライクめっき液中において、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５００ｒｐｍで撹拌しながら電流密度２Ａ／ｄｍ２で１０秒間電気めっき（銀ストライクめっき）を行った後、１５秒間水洗した。 Next, in a silver strike plating solution consisting of an aqueous solution containing 3 g / L of silver cyanide potassium and 90 g / L of potassium cyanide, the material to be plated is a cathode and the titanium electrode plate coated with platinum is an anode, and 500 rpm by a stirrer. After electroplating (silver strike plating) was performed at a current density of 2 A / dm 2 for 10 seconds while stirring with water, the plate was washed with water for 15 seconds.
次に、２０３ｇ／Ｌのシアン化銀カリウム（ＫＡｇ（ＣＮ）２）と、７０ｇ／Ｌのシアン化カリウム（ＫＣＮ）と、１２８ｍｇ／Ｌのセレノシアン酸カリウム（ＫＳｅＣＮ）と、１１５ｇ／Ｌの炭酸カリウム（Ｋ２ＣＯ３）とを含む水溶液からなる銀めっき液中において、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５００ｒｐｍで撹拌しながら液温２４℃において電流密度１０Ａ／ｄｍ２で銀めっき皮膜の厚さが５μｍになるまで電気めっき（銀めっき）を行った後、１５秒間水洗し、エアガンによる風圧で乾燥した。なお、使用した銀めっき液中のＡｇ濃度は１１０ｇ／Ｌ、ＫＣＮ濃度は７０ｇ／Ｌ、Ｓｅ濃度は７０ｍｇ／Ｌ、炭酸カリウム濃度は１１５ｇ／Ｌである。 Next, 203 g / L of silver potassium cyanide (KAg (CN) 2 ), 70 g / L of potassium cyanide (KCN), 128 mg / L of potassium selenocyanate (KSeCN), and 115 g / L of potassium carbonate (K In a silver plating solution consisting of an aqueous solution containing 2 CO 3 ), the material to be plated is a cathode and the silver electrode plate is an anode, and silver is stirred at a current density of 10 A / dm 2 at 24 ° C. After electroplating (silver plating) was performed until the thickness of the plating film became 5 μm, the plate was washed with water for 15 seconds and dried by an air gun. The Ag concentration in the silver plating solution used is 110 g / L, the KCN concentration is 70 g / L, the Se concentration is 70 mg / L, and the potassium carbonate concentration is 115 g / L.
このようにして得られた銀めっき材を乾燥機（アズワン社製のＯＦ４５０）により大気中において５０℃で１６８時間（１週間）加熱する耐熱試験を行った後、ビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１２２であり、耐熱試験前より低くなったものの、十分に高かった。なお、銀めっき材のビッカース硬さＨｖは、微小硬さ試験機（株式会社ミツトヨ製のＨＭ−２２１）を使用し、測定荷重１０ｇｆを１０秒間加えて、ＪＩＳ Ｚ２２４４に準じて測定した。 A heat resistance test was conducted to heat the silver-plated product obtained in this manner with an oven (OF450 manufactured by As One Corporation) at 50 ° C. for 168 hours (one week) in the atmosphere, and then the Vickers hardness Hv was measured. The Vickers hardness Hv after the heat resistance test was 122, which was lower than before the heat resistance test, but was sufficiently high. The Vickers hardness Hv of the silver-plated product was measured according to JIS Z2244 using a microhardness tester (HM-221 manufactured by Mitutoyo Co., Ltd.) and applying a measurement load of 10 gf for 10 seconds.
また、電気接点シミュレータ（山崎精機研究所製のＣＲＳ−１）により、銀めっき材の板面上にＲ＝１の半球形状にインデント加工した銀めっき材を荷重３００ｇｆで押し当てながら、摺動速度１００ｍｍ／分で摺動距離５ｍｍとして１回摺動させたときの接触抵抗を測定したところ、接触抵抗は０．６ｍΩ以下と低かった。 In addition, a sliding speed is applied while pressing a silver plating material indented into a hemispherical shape of R = 1 on a plate surface of a silver plating material with an electric contact simulator (CRS-1 manufactured by Yamazaki Seiki Laboratory) with a load of 300 gf When the contact resistance was measured at a sliding distance of 5 mm at a sliding distance of 5 mm at 100 mm / min, the contact resistance was as low as 0.6 mΩ or less.
また、銀めっき材の光沢度として、濃度計（日本電色株式会社製のデントシメーターＮＤ−１）を用いて、素材の圧延方向に対して平行に銀めっき材の反射濃度を測定したところ、１．６７であり、光沢度は良好であった。 In addition, when the reflection density of the silver plating material was measured in parallel to the rolling direction of the material using a densitometer (Dentometer SI manufactured by Nippon Denshoku Co., Ltd.) as the glossiness of the silver plating material , 1.67 and the gloss was good.
また、銀めっき材の銀めっき皮膜を硝酸に溶かして液体にした後、溶液の濃度を調整し、ＩＣＰ発光分光分析（ＩＣＰ−ＯＥＳ）装置（セイコーインスツル株式会社製のＳＰＳ５１００）を使用してプラズマ分光分析によりＡｇ純度を求めたところ、９９．９質量％以上であった。 In addition, after the silver plating film of the silver plating material is dissolved in nitric acid to make a liquid, the concentration of the solution is adjusted, and an ICP emission spectral analysis (ICP-OES) apparatus (SPS5100 manufactured by Seiko Instruments Inc.) is used. When Ag purity was calculated | required by plasma spectroscopy, it was 99.9 mass% or more.
［実施例２］
液温２７℃で電気めっき（銀めっき）を行った以外は、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
The silver plating material was produced by the same method as Example 1 except having performed electroplating (silver plating) at 27 ° C of solution temperature.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験後の銀めっき材のビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１２５であり、耐熱試験前より低くなったものの、十分に高かった。 The Vickers hardness Hv of the silver-plated material after the heat test was measured by the same method as in Example 1 for the silver-plated material thus obtained, and the Vickers hardness Hv after the heat test is 125. Although it was lower than before the heat resistance test, it was sufficiently high.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．６ｍΩ以下と低かった。また、銀めっき材の反射濃度は１．６２であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.6 mΩ or less. Further, the reflection density of the silver-plated product was 1.62, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［実施例３］
液温３０℃で電気めっき（銀めっき）を行った以外は、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]
The silver plating material was produced by the same method as Example 1 except having performed electroplating (silver plating) at liquid temperature of 30 ° C.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験後のビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１４７であり、耐熱試験前より低くなったものの、十分に高かった。 The Vickers hardness Hv after the heat resistance test of the silver-plated material thus obtained was measured by the same method as in Example 1. The Vickers hardness Hv after the heat resistance test is 147, which is before the heat resistance test. Although it was lower, it was high enough.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．６ｍΩ以下と低かった。また、銀めっき材の反射濃度は１．２４であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.6 mΩ or less. Further, the reflection density of the silver-plated product was 1.24 and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［実施例４］
液温３３℃で電気めっき（銀めっき）を行った以外は、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
The silver plating material was produced by the same method as Example 1 except having performed electroplating (silver plating) at liquid temperature 33 ° C.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験後の銀めっき材のビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１４２であり、耐熱試験前より低くなったものの、十分に高かった。 The Vickers hardness Hv of the silver-plated material after the heat test was measured by the same method as in Example 1 for the silver-plated material thus obtained, and the Vickers hardness Hv after the heat test is 142. Although it was lower than before the heat resistance test, it was sufficiently high.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．６ｍΩ以下と低かった。また、銀めっき材の反射濃度は０．３９であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.6 mΩ or less. Further, the reflection density of the silver-plated product was 0.39, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［実施例５］
銀めっき液中の炭酸カリウムの量を１５０ｇ／Ｌ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。なお、使用した銀めっき液中のＡｇ濃度は１１０ｇ／Ｌ、ＫＣＮ濃度は７０ｇ／Ｌ、Ｓｅ濃度は７０ｍｇ／Ｌ、炭酸カリウム濃度は１５０ｇ／Ｌである。
[Example 5]
A silver plating material was produced in the same manner as in Example 1 except that the amount of potassium carbonate in the silver plating solution was changed to 150 g / L. The Ag concentration in the silver plating solution used is 110 g / L, the KCN concentration is 70 g / L, the Se concentration is 70 mg / L, and the potassium carbonate concentration is 150 g / L.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験後の銀めっき材のビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１３４であり、耐熱試験前より低くなったものの、十分に高かった。 The Vickers hardness Hv of the silver-plated material after the heat test was measured by the same method as in Example 1 for the silver-plated material thus obtained, and the Vickers hardness Hv after the heat test is 134. Although it was lower than before the heat resistance test, it was sufficiently high.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．６ｍΩ以下と低かった。また、銀めっき材の反射濃度は１．７６であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.6 mΩ or less. In addition, the reflection density of the silver-plated product was 1.76, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［実施例６］
液温２７℃で電気めっき（銀めっき）を行った以外は、実施例５と同様の方法により、銀めっき材を作製した。
[Example 6]
A silver-plated product was produced in the same manner as in Example 5 except that electroplating (silver plating) was performed at a solution temperature of 27 ° C.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験後の銀めっき材のビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１３１であり、耐熱試験前より低くなったものの、十分に高かった The Vickers hardness Hv of the silver-plated material after the heat test was measured by the same method as in Example 1 for the silver-plated material thus obtained, and the Vickers hardness Hv after the heat test is 131. Although it was lower than before the heat resistance test, it was high enough
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．６ｍΩ以下と低かった。また、銀めっき材の反射濃度は１．６７であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.6 mΩ or less. In addition, the reflection density of the silver-plated product was 1.67, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［実施例７］
液温３０℃で電気めっき（銀めっき）を行った以外は、実施例５と同様の方法により、銀めっき材を作製した。
[Example 7]
The silver plating material was produced by the same method as Example 5 except having performed electroplating (silver plating) at liquid temperature of 30 ° C.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験後の銀めっき材のビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１２４であり、耐熱試験前より低くなったものの、十分に高かった。 The Vickers hardness Hv of the silver-plated material after the heat test was measured by the same method as in Example 1 for the silver-plated material thus obtained, and the Vickers hardness Hv after the heat test is 124. Although it was lower than before the heat resistance test, it was sufficiently high.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．６ｍΩ以下と低かった。また、銀めっき材の反射濃度は１．６４であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.6 mΩ or less. In addition, the reflection density of the silver-plated product was 1.64 and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［実施例８］
液温３３℃で電気めっき（銀めっき）を行った以外は、実施例５と同様の方法により、銀めっき材を作製した。
[Example 8]
The silver plating material was produced by the same method as Example 5 except having performed electroplating (silver plating) at liquid temperature 33 ° C.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験後の銀めっき材のビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１４５であり、耐熱試験前より低くなったものの、十分に高かった。 The Vickers hardness Hv of the silver-plated product after the heat test was measured by the same method as in Example 1 for the silver-plated product thus obtained. The Vickers hardness Hv after the heat test is 145. Although it was lower than before the heat resistance test, it was sufficiently high.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．６ｍΩ以下と低かった。また、銀めっき材の反射濃度は１．５５であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.6 mΩ or less. Further, the reflection density of the silver-plated product was 1.55, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［実施例９］
液温３６℃で電気めっき（銀めっき）を行った以外は、実施例５と同様の方法により、銀めっき材を作製した。
[Example 9]
A silver-plated product was produced in the same manner as in Example 5 except that electroplating (silver plating) was performed at a solution temperature of 36 ° C.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験後の銀めっき材のビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１３７であり、耐熱試験前より低くなったものの、十分に高かった。 The Vickers hardness Hv of the silver-plated product after the heat test was measured by the same method as in Example 1 for the silver-plated product thus obtained. The Vickers hardness Hv after the heat test is 137. Although it was lower than before the heat resistance test, it was sufficiently high.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．６ｍΩ以下と低かった。また、銀めっき材の反射濃度は０．４２であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.6 mΩ or less. Further, the reflection density of the silver-plated product was 0.42, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［実施例１０］
１７５ｇ／Ｌのシアン化銀カリウムと、１２０ｇ／Ｌのシアン化カリウムと、７３ｍｇ／Ｌのセレノシアン酸カリウムと、９２ｇ／Ｌの炭酸カリウムとを含む水溶液からなる銀めっき液中において、液温２４℃、電流密度５Ａ／ｄｍ２で電気めっき（銀めっき）を行った以外は、実施例１と同様の方法により、銀めっき材を作製した。なお、使用した銀めっき液中のＡｇ濃度は９５ｇ／Ｌ、ＫＣＮ濃度は１２０ｇ／Ｌ、Ｓｅ濃度は４０ｍｇ／Ｌ、炭酸カリウム濃度は９２ｇ／Ｌである。
[Example 10]
In a silver plating solution composed of an aqueous solution containing 175 g / L of silver cyanide potassium, 120 g / L of potassium cyanide, 73 mg / L of potassium selenocyanate, and 92 g / L of potassium carbonate, the solution temperature is 24 ° C., the current except that a density 5A / dm 2 was electroplated (silver plating) is in the same manner as in example 1 to prepare a silver-plated material. The Ag concentration in the silver plating solution used is 95 g / L, the KCN concentration is 120 g / L, the Se concentration is 40 mg / L, and the potassium carbonate concentration is 92 g / L.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験後の銀めっき材のビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１３０であり、耐熱試験前より低くなったものの、十分に高かった。 The Vickers hardness Hv of the silver-plated material after the heat test was measured by the same method as in Example 1 for the silver-plated material thus obtained, and the Vickers hardness Hv after the heat test is 130. Although it was lower than before the heat resistance test, it was sufficiently high.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．６ｍΩ以下と低かった。また、銀めっき材の反射濃度は０．３以上であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.6 mΩ or less. Further, the reflection density of the silver-plated product was 0.3 or more, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［実施例１１］
電流密度６Ａ／ｄｍ２で電気めっき（銀めっき）を行った以外は、実施例１０と同様の方法により、銀めっき材を作製した。
[Example 11]
A silver-plated product was produced in the same manner as in Example 10 except that electroplating (silver plating) was performed at a current density of 6 A / dm 2 .
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験後の銀めっき材のビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１３３であり、耐熱試験前より低くなったものの、十分に高かった。 The Vickers hardness Hv of the silver-plated material after the heat test was measured by the same method as in Example 1 for the silver-plated material thus obtained, and the Vickers hardness Hv after the heat test is 133. Although it was lower than before the heat resistance test, it was sufficiently high.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．６ｍΩ以下と低かった。また、銀めっき材の反射濃度は０．３以上であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.6 mΩ or less. Further, the reflection density of the silver-plated product was 0.3 or more, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［実施例１２］
電流密度７Ａ／ｄｍ２で電気めっき（銀めっき）を行った以外は、実施例１０と同様の方法により、銀めっき材を作製した。
[Example 12]
A silver-plated product was produced in the same manner as in Example 10 except that electroplating (silver plating) was performed at a current density of 7 A / dm 2 .
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験後の銀めっき材のビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１２８であり、耐熱試験前より低くなったものの、十分に高かった。 The Vickers hardness Hv of the silver-plated material after the heat test was measured by the same method as in Example 1 for the silver-plated material thus obtained, and the Vickers hardness Hv after the heat test is 128. Although it was lower than before the heat resistance test, it was sufficiently high.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．６ｍΩ以下と低かった。また、銀めっき材の反射濃度は０．３以上であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.6 mΩ or less. Further, the reflection density of the silver-plated product was 0.3 or more, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［実施例１３］
電流密度８Ａ／ｄｍ２で電気めっき（銀めっき）を行った以外は、実施例１０と同様の方法により、銀めっき材を作製した。
[Example 13]
A silver-plated product was produced in the same manner as in Example 10 except that electroplating (silver plating) was performed at a current density of 8 A / dm 2 .
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験後の銀めっき材のビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１２４であり、耐熱試験前より低くなったものの、十分に高かった。 The Vickers hardness Hv of the silver-plated material after the heat test was measured by the same method as in Example 1 for the silver-plated material thus obtained, and the Vickers hardness Hv after the heat test is 124. Although it was lower than before the heat resistance test, it was sufficiently high.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．６ｍΩ以下と低かった。また、銀めっき材の反射濃度は０．３以上であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.6 mΩ or less. Further, the reflection density of the silver-plated product was 0.3 or more, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［実施例１４］
銀めっき液中の炭酸カリウムの量を１３８ｇ／Ｌとし、電流密度４Ａ／ｄｍ２で電気めっき（銀めっき）を行った以外は、実施例１０と同様の方法により、銀めっき材を作製した。なお、使用した銀めっき液中のＡｇ濃度は９５ｇ／Ｌ、ＫＣＮ濃度は１２０ｇ／Ｌ、Ｓｅ濃度は４０ｍｇ／Ｌ、炭酸カリウム濃度は１３８ｇ／Ｌである。
Example 14
A silver plating material was produced in the same manner as in Example 10 except that the amount of potassium carbonate in the silver plating solution was 138 g / L and electroplating (silver plating) was performed at a current density of 4 A / dm 2 . The Ag concentration in the silver plating solution used is 95 g / L, the KCN concentration is 120 g / L, the Se concentration is 40 mg / L, and the potassium carbonate concentration is 138 g / L.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験後の銀めっき材のビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１３２であり、耐熱試験前より低くなったものの、十分に高かった。 The Vickers hardness Hv of the silver-plated product after the heat test was measured by the same method as in Example 1 for the silver-plated product thus obtained. The Vickers hardness Hv after the heat test is 132. Although it was lower than before the heat resistance test, it was sufficiently high.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．６ｍΩ以下と低かった。また、銀めっき材の反射濃度は０．３以上であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.6 mΩ or less. Further, the reflection density of the silver-plated product was 0.3 or more, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［実施例１５］
電流密度５Ａ／ｄｍ２で電気めっき（銀めっき）を行った以外は、実施例１４と同様の方法により、銀めっき材を作製した。
[Example 15]
A silver-plated product was produced in the same manner as in Example 14 except that electroplating (silver plating) was performed at a current density of 5 A / dm 2 .
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験後の銀めっき材のビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１３４であり、耐熱試験前より低くなったものの、十分に高かった。 The Vickers hardness Hv of the silver-plated material after the heat test was measured by the same method as in Example 1 for the silver-plated material thus obtained, and the Vickers hardness Hv after the heat test is 134. Although it was lower than before the heat resistance test, it was sufficiently high.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．６ｍΩ以下と低かった。また、銀めっき材の反射濃度は０．３以上であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.6 mΩ or less. Further, the reflection density of the silver-plated product was 0.3 or more, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［実施例１６］
電流密度６Ａ／ｄｍ２で電気めっき（銀めっき）を行った以外は、実施例１４と同様の方法により、銀めっき材を作製した。
[Example 16]
A silver-plated product was produced in the same manner as in Example 14 except that electroplating (silver plating) was performed at a current density of 6 A / dm 2 .
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験後の銀めっき材のビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１３０であり、耐熱試験前より低くなったものの、十分に高かった。 The Vickers hardness Hv of the silver-plated material after the heat test was measured by the same method as in Example 1 for the silver-plated material thus obtained, and the Vickers hardness Hv after the heat test is 130. Although it was lower than before the heat resistance test, it was sufficiently high.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．６ｍΩ以下と低かった。また、銀めっき材の反射濃度は０．３以上であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.6 mΩ or less. Further, the reflection density of the silver-plated product was 0.3 or more, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［実施例１７］
電流密度７Ａ／ｄｍ２で電気めっき（銀めっき）を行った以外は、実施例１４と同様の方法により、銀めっき材を作製した。
[Example 17]
A silver-plated product was produced in the same manner as in Example 14 except that electroplating (silver plating) was performed at a current density of 7 A / dm 2 .
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験後の銀めっき材のビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１２３であり、耐熱試験前より低くなったものの、十分に高かった。 The Vickers hardness Hv of the silver-plated product after the heat test was measured by the same method as in Example 1 for the silver-plated product thus obtained, and the Vickers hardness Hv after the heat test is 123. Although it was lower than before the heat resistance test, it was sufficiently high.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．６ｍΩ以下と低かった。また、銀めっき材の反射濃度は０．３以上であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.6 mΩ or less. Further, the reflection density of the silver-plated product was 0.3 or more, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［比較例１］
１４８ｇ／Ｌのシアン化銀カリウムと７０ｇ／Ｌのシアン化カリウムと１０９ｍｇ／Ｌのセレノシアン酸カリウムを含む（炭酸カリウムを含まない）水溶液からなる銀めっき液中において、液温１８℃、電流密度３Ａ／ｄｍ２で電気めっき（銀めっき）を行った以外は、実施例１と同様の方法により、銀めっき材を作製した。なお、使用した銀めっき液中のＡｇ濃度は８０ｇ／Ｌ、ＫＣＮ濃度は７０ｇ／Ｌ、Ｓｅ濃度は６０ｍｇ／Ｌである。
Comparative Example 1
In a silver plating solution consisting of an aqueous solution (containing no potassium carbonate) containing 148 g / L of silver potassium cyanide, 70 g / L of potassium cyanide and 109 mg / L of potassium selenocyanate, the liquid temperature is 18 ° C., the current density is 3 A / dm A silver plating material was produced in the same manner as in Example 1 except that the electroplating (silver plating) was performed in 2 . The Ag concentration in the silver plating solution used is 80 g / L, the KCN concentration is 70 g / L, and the Se concentration is 60 mg / L.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験前後のビッカース硬さＨｖを測定したところ、耐熱試験前のビッカース硬さＨｖは１１２であり、耐熱試験後のビッカース硬さＨｖは１０８であった。 When the Vickers hardness Hv before and after the heat resistance test was measured by the same method as in Example 1 for the silver-plated product thus obtained, the Vickers hardness Hv before the heat resistance test is 112, and after the heat resistance test The Vickers hardness Hv of was 108.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．１４ｍΩと低かった。また、銀めっき材の反射濃度は０．０７であり、光沢度は良好でなかった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.14 mΩ. In addition, the reflection density of the silver-plated product was 0.07, and the glossiness was not good. Moreover, Ag purity was 99.9 mass% or more.
［比較例２］
１４８ｇ／Ｌのシアン化銀カリウムと１６０ｇ／Ｌのシアン化カリウムと１０９ｍｇ／Ｌのセレノシアン酸カリウムを含む（炭酸カリウムを含まない）水溶液からなる銀めっき液中において、液温１８℃、電流密度５Ａ／ｄｍ２で電気めっき（銀めっき）を行った以外は、実施例１と同様の方法により、銀めっき材を作製した。なお、使用した銀めっき液中のＡｇ濃度は８０ｇ／Ｌ、ＫＣＮ濃度は１６０ｇ／Ｌ、Ｓｅ濃度は６０ｍｇ／Ｌである。
Comparative Example 2
In a silver plating solution consisting of an aqueous solution (containing no potassium carbonate) containing 148 g / L of silver potassium cyanide, 160 g / L of potassium cyanide and 109 mg / L of potassium selenocyanate, the liquid temperature is 18 ° C., the current density is 5 A / dm A silver plating material was produced in the same manner as in Example 1 except that the electroplating (silver plating) was performed in 2 . The Ag concentration in the silver plating solution used is 80 g / L, the KCN concentration is 160 g / L, and the Se concentration is 60 mg / L.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験前後のビッカース硬さＨｖを測定したところ、耐熱試験前のビッカース硬さＨｖは１２４であり、 耐熱試験後のビッカース硬さＨｖは９５であった。 The Vickers hardness Hv before and after the heat resistance test of the silver-plated material thus obtained was measured by the same method as in Example 1. The Vickers hardness Hv before the heat resistance test is 124, and the heat resistance test is performed. The Vickers hardness Hv of was 95.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．４４ｍΩと低かった。また、銀めっき材の反射濃度は１．５８であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.44 mΩ. Further, the reflection density of the silver-plated product was 1.58, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［比較例３］
１４８ｇ／Ｌのシアン化銀カリウムと１６０ｇ／Ｌのシアン化カリウムと１０９ｍｇ／Ｌのセレノシアン酸カリウムを含む（炭酸カリウムを含まない）水溶液からなる銀めっき液中において、液温１８℃、電流密度７Ａ／ｄｍ２で電気めっき（銀めっき）を行った以外は、実施例１と同様の方法により、銀めっき材を作製した。なお、使用した銀めっき液中のＡｇ濃度は８０ｇ／Ｌ、ＫＣＮ濃度は１６０ｇ／Ｌ、Ｓｅ濃度は６０ｍｇ／Ｌである。
Comparative Example 3
In a silver plating solution consisting of an aqueous solution (without potassium carbonate) containing 148 g / L of silver cyanide potassium, 160 g / L of potassium cyanide and 109 mg / L of potassium selenocyanate, the solution temperature is 18 ° C., the current density is 7 A / dm A silver plating material was produced in the same manner as in Example 1 except that the electroplating (silver plating) was performed in 2 . The Ag concentration in the silver plating solution used is 80 g / L, the KCN concentration is 160 g / L, and the Se concentration is 60 mg / L.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験前後のビッカース硬さＨｖを測定したところ、耐熱試験前のビッカース硬さＨｖは１２０であり、 耐熱試験後のビッカース硬さＨｖは１０４であった。 The Vickers hardness Hv before and after the heat resistance test of the silver-plated product thus obtained was measured by the same method as in Example 1. The Vickers hardness Hv before the heat resistance test is 120, and the heat resistance test is performed. The Vickers hardness Hv of was 104.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．１９ｍΩと低かった。また、銀めっき材の反射濃度は１．６５であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.19 mΩ. In addition, the reflection density of the silver-plated product was 1.65, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［比較例４］
１３８ｇ／Ｌのシアン化銀カリウムと１４０ｇ／Ｌのシアン化カリウムと１１ｍｇ／Ｌのセレノシアン酸カリウムを含む（炭酸カリウムを含まない）水溶液からなる銀めっき液中において、液温１８℃、電流密度５Ａ／ｄｍ２で電気めっき（銀めっき）を行った以外は、実施例１と同様の方法により、銀めっき材を作製した。なお、使用した銀めっき液中のＡｇ濃度は７５ｇ／Ｌ、ＫＣＮ濃度は１４０ｇ／Ｌ、Ｓｅ濃度は６ｍｇ／Ｌである。
Comparative Example 4
In a silver plating solution consisting of an aqueous solution (containing no potassium carbonate) containing 138 g / L of silver potassium cyanide, 140 g / L of potassium cyanide and 11 mg / L of potassium selenocyanate, the solution temperature is 18 ° C., the current density is 5 A / dm A silver plating material was produced in the same manner as in Example 1 except that the electroplating (silver plating) was performed in 2 . The Ag concentration in the silver plating solution used is 75 g / L, the KCN concentration is 140 g / L, and the Se concentration is 6 mg / L.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験前後のビッカース硬さＨｖを測定したところ、耐熱試験前のビッカース硬さＨｖは１３１であり、 耐熱試験後のビッカース硬さＨｖは８４であった。 The Vickers hardness Hv before and after the heat resistance test of the silver-plated material thus obtained was measured by the same method as in Example 1. The Vickers hardness Hv before the heat resistance test is 131, and after the heat resistance test The Vickers hardness Hv of was 84.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．１２ｍΩと低かった。また、銀めっき材の反射濃度は１．６３であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.12 mΩ. Moreover, the reflection density of the silver plating material was 1.63, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［比較例５］
５５ｇ／Ｌのシアン化銀カリウムと１５０ｇ／Ｌのシアン化カリウムと３ｍｇ／Ｌの二酸化セレンと１７９４ｍｇ／Ｌの三酸化アンチモンを含む（炭酸カリウムを含まない）水溶液からなる銀めっき液中において、液温１５℃、電流密度３Ａ／ｄｍ２で電気めっき（銀めっき）を行った以外は、実施例１と同様の方法により、銀めっき材を作製した。なお、使用した銀めっき液中のＡｇ濃度は３０ｇ／Ｌ、ＫＣＮ濃度は１５０ｇ／Ｌ、Ｓｅ濃度は２ｍｇ／Ｌ、Ｓｂ濃度は７５０ｍｇ／Ｌである。
Comparative Example 5
The solution temperature is 15 in a silver plating solution consisting of an aqueous solution containing 55 g / L of silver cyanide potassium, 150 g / L of potassium cyanide, 3 mg / L of selenium dioxide and 1794 mg / L of antimony trioxide (without potassium carbonate). A silver-plated product was produced in the same manner as in Example 1 except that electroplating (silver plating) was performed at a current density of 3 A / dm 2 and a temperature of 3 ° C. The Ag concentration in the silver plating solution used is 30 g / L, the KCN concentration is 150 g / L, the Se concentration is 2 mg / L, and the Sb concentration is 750 mg / L.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験前後のビッカース硬さＨｖを測定したところ、耐熱試験前のビッカース硬さＨｖは１６１であり、 耐熱試験後のビッカース硬さＨｖは１６６であった。 The Vickers hardness Hv before and after the heat resistance test of the silver-plated product thus obtained was measured by the same method as in Example 1. The Vickers hardness Hv before the heat resistance test is 161, and the heat resistance test is performed. The Vickers hardness Hv of was 166.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は１０．５６ｍΩと高かった。また、銀めっき材の反射濃度は１．８１であり、光沢度は良好であった。また、Ａｇ純度は９８．４質量％であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as high as 10.56 mΩ. Further, the reflection density of the silver-plated product was 1.81, and the glossiness was good. Moreover, Ag purity was 98.4 mass%.
［比較例６］
１７５ｇ／Ｌのシアン化銀カリウムと７０ｇ／Ｌのシアン化カリウムと１２８ｍｇ／Ｌのセレノシアン酸カリウムを含む（炭酸カリウムを含まない）水溶液からなる銀めっき液中において、液温１２℃、電流密度１Ａ／ｄｍ２で電気めっき（銀めっき）を行った以外は、実施例１と同様の方法により、銀めっき材を作製した。なお、使用した銀めっき液中のＡｇ濃度は９５ｇ／Ｌ、ＫＣＮ濃度は７０ｇ／Ｌ、Ｓｅ濃度は７０ｍｇ／Ｌである。
Comparative Example 6
In a silver plating solution consisting of an aqueous solution (containing no potassium carbonate) containing 175 g / L potassium silver cyanide, 70 g / L potassium cyanide and 128 mg / L potassium selenocyanate, the solution temperature is 12 ° C., the current density is 1 A / dm A silver plating material was produced in the same manner as in Example 1 except that the electroplating (silver plating) was performed in 2 . The Ag concentration in the silver plating solution used is 95 g / L, the KCN concentration is 70 g / L, and the Se concentration is 70 mg / L.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験前後のビッカース硬さＨｖを測定したところ、耐熱試験前のビッカース硬さＨｖは１２１であり、 耐熱試験後のビッカース硬さＨｖは１１７であった。 The Vickers hardness Hv before and after the heat resistance test of the silver-plated product thus obtained was measured by the same method as in Example 1. The Vickers hardness Hv before the heat resistance test is 121, and the heat resistance test is performed. The Vickers hardness Hv of was 117.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．１９ｍΩと低かった。また、銀めっき材の反射濃度は０．０７であり、光沢度は良好でなかった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.19 mΩ. In addition, the reflection density of the silver-plated product was 0.07, and the glossiness was not good. Moreover, Ag purity was 99.9 mass% or more.
［比較例７］
１７５ｇ／Ｌのシアン化銀カリウムと９５ｇ／Ｌのシアン化カリウムと１００ｍｇ／Ｌのセレノシアン酸カリウムを含む（炭酸カリウムを含まない）水溶液からなる銀めっき液中において、液温１２℃、電流密度８Ａ／ｄｍ２で電気めっき（銀めっき）を行った以外は、実施例１と同様の方法により、銀めっき材を作製した。なお、使用した銀めっき液中のＡｇ濃度は９５ｇ／Ｌ、ＫＣＮ濃度は９５ｇ／Ｌ、Ｓｅ濃度は５５ｍｇ／Ｌである。
Comparative Example 7
In a silver plating solution composed of an aqueous solution (containing no potassium carbonate) containing 175 g / L potassium silver cyanide, 95 g / L potassium cyanide and 100 mg / L potassium selenocyanate, the liquid temperature is 12 ° C., the current density 8 A / dm A silver plating material was produced in the same manner as in Example 1 except that the electroplating (silver plating) was performed in 2 . The Ag concentration in the silver plating solution used is 95 g / L, the KCN concentration is 95 g / L, and the Se concentration is 55 mg / L.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験前後のビッカース硬さＨｖを測定したところ、耐熱試験前のビッカース硬さＨｖは１３８であり、 耐熱試験後のビッカース硬さＨｖは９５であった。 The Vickers hardness Hv before and after the heat resistance test of the silver-plated material thus obtained was measured by the same method as in Example 1. The Vickers hardness Hv before the heat resistance test is 138, and the heat resistance test is performed. The Vickers hardness Hv of was 95.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．２５ｍΩと低かった。また、銀めっき材の反射濃度は０．６であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.25 mΩ. Moreover, the reflection density of the silver plating material was 0.6, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［比較例８］
１７５ｇ／Ｌのシアン化銀カリウムと７０ｇ／Ｌのシアン化カリウムと１２８ｍｇ／Ｌのセレノシアン酸カリウムを含む（炭酸カリウムを含まない）水溶液からなる銀めっき液中において、液温２４℃、電流密度６Ａ／ｄｍ２で電気めっき（銀めっき）を行った以外は、実施例１と同様の方法により、銀めっき材を作製した。なお、使用した銀めっき液中のＡｇ濃度は９５ｇ／Ｌ、ＫＣＮ濃度は７０ｇ／Ｌ、Ｓｅ濃度は７０ｍｇ／Ｌである。
Comparative Example 8
In a silver plating solution consisting of an aqueous solution (containing no potassium carbonate) containing 175 g / L of silver potassium cyanide, 70 g / L of potassium cyanide and 128 mg / L of potassium selenocyanate, the liquid temperature 24 ° C., current density 6 A / dm A silver plating material was produced in the same manner as in Example 1 except that the electroplating (silver plating) was performed in 2 . The Ag concentration in the silver plating solution used is 95 g / L, the KCN concentration is 70 g / L, and the Se concentration is 70 mg / L.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験前後のビッカース硬さＨｖを測定したところ、耐熱試験前のビッカース硬さＨｖは１２０であり、 耐熱試験後のビッカース硬さＨｖは１０９であった。 The Vickers hardness Hv before and after the heat resistance test of the silver-plated product thus obtained was measured by the same method as in Example 1. The Vickers hardness Hv before the heat resistance test is 120, and the heat resistance test is performed. The Vickers hardness Hv of was 109.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．２５ｍΩと低かった。また、銀めっき材の反射濃度０．０９であり、光沢度は良好でなかった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.25 mΩ. In addition, the reflection density of the silver-plated product was 0.09, and the glossiness was not good. Moreover, Ag purity was 99.9 mass% or more.
［比較例９］
１７５ｇ／Ｌのシアン化銀カリウムと９５ｇ／Ｌのシアン化カリウムと１００ｍｇ／Ｌのセレノシアン酸カリウムを含む（炭酸カリウムを含まない）水溶液からなる銀めっき液中において、液温２４℃、電流密度１２Ａ／ｄｍ２で電気めっき（銀めっき）を行った以外は、実施例１と同様の方法により、銀めっき材を作製した。なお、使用した銀めっき液中のＡｇ濃度は９５ｇ／Ｌ、ＫＣＮ濃度は９５ｇ／Ｌ、Ｓｅ濃度は５５ｍｇ／Ｌである。
Comparative Example 9
In a silver plating solution consisting of an aqueous solution (containing no potassium carbonate) containing 175 g / L potassium silver cyanide, 95 g / L potassium cyanide and 100 mg / L potassium selenocyanate, the liquid temperature is 24 ° C., the current density 12 A / dm A silver plating material was produced in the same manner as in Example 1 except that the electroplating (silver plating) was performed in 2 . The Ag concentration in the silver plating solution used is 95 g / L, the KCN concentration is 95 g / L, and the Se concentration is 55 mg / L.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験前後のビッカース硬さＨｖを測定したところ、耐熱試験前のビッカース硬さＨｖは１３５であり、 耐熱試験後のビッカース硬さＨｖは１０６であった。 The Vickers hardness Hv before and after the heat resistance test of the silver-plated material thus obtained was measured by the same method as in Example 1. The Vickers hardness Hv before the heat resistance test is 135, and the heat resistance test is performed. The Vickers hardness Hv of was 106.
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．４５ｍΩと低かった。また、銀めっき材の反射濃度は１．５８であり、光沢度は良好であった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.45 mΩ. Further, the reflection density of the silver-plated product was 1.58, and the glossiness was good. Moreover, Ag purity was 99.9 mass% or more.
［比較例１０］
２０３ｇ／Ｌのシアン化銀カリウムと７０ｇ／Ｌのシアン化カリウムと１２８ｍｇ／Ｌのセレノシアン酸カリウムを含む（炭酸カリウムを含まない）水溶液からなる銀めっき液中において、液温３３℃で電気めっき（銀めっき）を行った以外は、実施例１と同様の方法により、銀めっき材を作製した。なお、使用した銀めっき液中のＡｇ濃度は１１０ｇ／Ｌ、ＫＣＮ濃度は７０ｇ／Ｌ、Ｓｅ濃度は７０ｍｇ／Ｌである。
Comparative Example 10
Electroplating at a temperature of 33 ° C. (silver plating) in a silver plating solution consisting of an aqueous solution (containing no potassium carbonate) containing 203 g / L of silver potassium cyanide, 70 g / L of potassium cyanide and 128 mg / L of potassium selenocyanate The silver plating material was produced by the same method as Example 1 except having carried out. The Ag concentration in the silver plating solution used is 110 g / L, the KCN concentration is 70 g / L, and the Se concentration is 70 mg / L.
このようにして得られた銀めっき材について、実施例１と同様の方法により、耐熱試験後の銀めっき材のビッカース硬さＨｖを測定したところ、耐熱試験後のビッカース硬さＨｖは１１２であった。 The Vickers hardness Hv of the silver-plated product after the heat test was measured by the same method as in Example 1 for the silver-plated product thus obtained. The Vickers hardness Hv after the heat test is 112. The
また、実施例１と同様の方法により、銀めっき材の接触抵抗および反射濃度を測定するとともに、Ａｇ純度を求めた。その結果、銀めっき材の接触抵抗は０．６ｍΩ以下と低かった。また、銀めっき材の反射濃度は０．０４であり、光沢度は良好でなかった。また、Ａｇ純度は９９．９質量％以上であった。 Further, the contact resistance and the reflection density of the silver-plated product were measured by the same method as in Example 1, and the Ag purity was determined. As a result, the contact resistance of the silver-plated product was as low as 0.6 mΩ or less. Moreover, the reflection density of the silver plating material was 0.04, and the glossiness was not good. Moreover, Ag purity was 99.9 mass% or more.
これらの実施例および比較例の銀めっき材の製造条件および特性を表１〜表２に示す。 The manufacturing conditions and characteristics of the silver-plated products of these examples and comparative examples are shown in Tables 1 and 2.
表１〜表２からわかるように、実施例１〜１７で製造した銀めっき材は、高い硬度を維持したまま、接触抵抗の増加を防止することができる。 As can be seen from Tables 1 and 2, the silver-plated products manufactured in Examples 1 to 17 can prevent an increase in contact resistance while maintaining high hardness.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018230536A JP6694941B2 (en) | 2018-12-10 | 2018-12-10 | Silver plated material and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018230536A JP6694941B2 (en) | 2018-12-10 | 2018-12-10 | Silver plated material and manufacturing method thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015090177A Division JP6450639B2 (en) | 2015-04-27 | 2015-04-27 | Silver plating material and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2019044274A true JP2019044274A (en) | 2019-03-22 |
| JP6694941B2 JP6694941B2 (en) | 2020-05-20 |
Family
ID=65816207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018230536A Active JP6694941B2 (en) | 2018-12-10 | 2018-12-10 | Silver plated material and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6694941B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020012202A (en) * | 2015-01-30 | 2020-01-23 | Ｄｏｗａメタルテック株式会社 | Silver plating material and method for producing the same |
| WO2020184227A1 (en) | 2019-03-11 | 2020-09-17 | キヤノン株式会社 | Image decoder, image decoding method, and program |
| US11211730B2 (en) * | 2019-05-16 | 2021-12-28 | Autonetworks Technologies, Ltd. | Connector terminal, electrical wire with terminal, and terminal pair |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09249977A (en) * | 1996-03-13 | 1997-09-22 | Nikko Kinzoku Kk | Surface treatment liquid for silver plated material and surface treatment using the same |
| JP2013076127A (en) * | 2011-09-30 | 2013-04-25 | Dowa Metaltech Kk | Silver plating material and production method therefor |
| JP2013189681A (en) * | 2012-03-14 | 2013-09-26 | Dowa Metaltech Kk | Silver plating material |
| JP6395560B2 (en) * | 2013-11-08 | 2018-09-26 | Ｄｏｗａメタルテック株式会社 | Silver plating material and method for producing the same |
-
2018
- 2018-12-10 JP JP2018230536A patent/JP6694941B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09249977A (en) * | 1996-03-13 | 1997-09-22 | Nikko Kinzoku Kk | Surface treatment liquid for silver plated material and surface treatment using the same |
| JP2013076127A (en) * | 2011-09-30 | 2013-04-25 | Dowa Metaltech Kk | Silver plating material and production method therefor |
| JP2013189681A (en) * | 2012-03-14 | 2013-09-26 | Dowa Metaltech Kk | Silver plating material |
| JP6395560B2 (en) * | 2013-11-08 | 2018-09-26 | Ｄｏｗａメタルテック株式会社 | Silver plating material and method for producing the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020012202A (en) * | 2015-01-30 | 2020-01-23 | Ｄｏｗａメタルテック株式会社 | Silver plating material and method for producing the same |
| WO2020184227A1 (en) | 2019-03-11 | 2020-09-17 | キヤノン株式会社 | Image decoder, image decoding method, and program |
| US11211730B2 (en) * | 2019-05-16 | 2021-12-28 | Autonetworks Technologies, Ltd. | Connector terminal, electrical wire with terminal, and terminal pair |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6694941B2 (en) | 2020-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6810229B2 (en) | Silver plating material and its manufacturing method | |
| US10597791B2 (en) | Silver-plated product and method for producing same | |
| JP6450639B2 (en) | Silver plating material and method for producing the same | |
| US9905951B2 (en) | Silver-plated product | |
| JP5667543B2 (en) | Silver plating material and method for producing the same | |
| JP2019044274A (en) | Silver plated material and method for producing the same | |
| EP2977489B1 (en) | Silver-plated material | |
| US20230097787A1 (en) | Silver-plated product and method for producing same | |
| WO2016121312A1 (en) | Silver-plated member and method for manufacturing same | |
| US10072348B2 (en) | Silver-plated product | |
| JP5209550B2 (en) | Silver plating material manufacturing method | |
| JP7455634B2 (en) | Silver plating material and its manufacturing method, and terminal parts | |
| JP6532323B2 (en) | Silver plating material and method for manufacturing the same | |
| WO2021181901A1 (en) | Silver-plated material and method for manufacturing same | |
| JP7083662B2 (en) | Plating material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20181210 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20181210 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190903 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20191002 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20191209 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20191223 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20200417 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20200420 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6694941 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |