JP6809856B2 - Silver plating material and its manufacturing method - Google Patents
Silver plating material and its manufacturing method Download PDFInfo
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- JP6809856B2 JP6809856B2 JP2016190882A JP2016190882A JP6809856B2 JP 6809856 B2 JP6809856 B2 JP 6809856B2 JP 2016190882 A JP2016190882 A JP 2016190882A JP 2016190882 A JP2016190882 A JP 2016190882A JP 6809856 B2 JP6809856 B2 JP 6809856B2
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- 239000000463 material Substances 0.000 title claims description 128
- 238000007747 plating Methods 0.000 title claims description 47
- 229910052709 silver Inorganic materials 0.000 title claims description 42
- 239000004332 silver Substances 0.000 title claims description 42
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 238000012360 testing method Methods 0.000 claims description 65
- 239000002344 surface layer Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 18
- 229930195729 fatty acid Natural products 0.000 claims description 18
- 239000000194 fatty acid Substances 0.000 claims description 18
- 150000004665 fatty acids Chemical class 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- 239000000839 emulsion Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 235000021355 Stearic acid Nutrition 0.000 claims description 14
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 14
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 14
- 239000008117 stearic acid Substances 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 10
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 8
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 5
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- -1 alkyl phosphate ester Chemical class 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- YWWVWXASSLXJHU-AATRIKPKSA-N (9E)-tetradecenoic acid Chemical compound CCCC\C=C\CCCCCCCC(O)=O YWWVWXASSLXJHU-AATRIKPKSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229960004232 linoleic acid Drugs 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 description 2
- GWHCXVQVJPWHRF-KTKRTIGZSA-N (15Z)-tetracosenoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCCCC(O)=O GWHCXVQVJPWHRF-KTKRTIGZSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- BMOKHTQIBPRXSL-UHFFFAOYSA-N 2h-benzotriazole;sodium Chemical compound [Na].C1=CC=CC2=NNN=C21 BMOKHTQIBPRXSL-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- YWWVWXASSLXJHU-UHFFFAOYSA-N 9E-tetradecenoic acid Natural products CCCCC=CCCCCCCCC(O)=O YWWVWXASSLXJHU-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- XJXROGWVRIJYMO-SJDLZYGOSA-N Nervonic acid Natural products O=C(O)[C@@H](/C=C/CCCCCCCC)CCCCCCCCCCCC XJXROGWVRIJYMO-SJDLZYGOSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel 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
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005452 bending Methods 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- GWHCXVQVJPWHRF-UHFFFAOYSA-N cis-tetracosenoic acid Natural products CCCCCCCCC=CCCCCCCCCCCCCCC(O)=O GWHCXVQVJPWHRF-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009429 electrical wiring Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001616 ion spectroscopy Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 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
- 229960002446 octanoic acid Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- HKSGQTYSSZOJOA-UHFFFAOYSA-N potassium argentocyanide Chemical compound [K+].[Ag+].N#[C-].N#[C-] HKSGQTYSSZOJOA-UHFFFAOYSA-N 0.000 description 1
- KYEKHFSRAXRJBR-UHFFFAOYSA-M potassium;selenocyanate Chemical compound [K+].[Se-]C#N KYEKHFSRAXRJBR-UHFFFAOYSA-M 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 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
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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 for manufacturing the same, and in particular, the silver-plated material used as a material for contacts and terminal parts such as connectors, switches, and relays used for in-vehicle and consumer electrical wiring and its manufacture. 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、銅または銅合金などの比較的安価で耐食性や機械的特性などに優れた基材に、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。 Conventionally, as a material for contacts and terminal parts such as connectors and switches, a relatively inexpensive base material such as copper or copper alloy with excellent corrosion resistance and mechanical properties is used, and necessary properties such as electrical properties and solderability are required. Depending on the situation, plating materials plated with tin, silver, gold, etc. are used.
銅または銅合金などの基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、これらの基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、これらの基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。 A tin-plated material obtained by tin-plating a base material such as copper or a copper alloy is inexpensive, but is inferior in corrosion resistance in a high-temperature environment. Further, the gold-plated material obtained by subjecting these base materials to gold plating has excellent corrosion resistance and high reliability, but the cost is high. On the other hand, the silver-plated material obtained by silver-plating these base materials is cheaper than the gold-plated material and has excellent corrosion resistance as compared with the tin-plated 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 abrasion resistance due to insertion and removal of connectors and sliding of switches.
しかし、銀めっき材は、軟質で摩耗し易いため、接続端子などの材料として使用すると、挿抜や摺動により凝着して凝着摩耗が生じ易くなり、また、接続端子の挿入時に表面が削られて摩擦係数が高くなって挿入力が高くなるという問題がある。特に、銀めっき材をワイヤーハーネスなどの挿抜可能なコネクタの材料として利用する場合に、繰り返しの挿抜によって銀めっき皮膜が削られて下地めっき皮膜や素地が露出すると、接触抵抗が増大して、発熱や発火に至るおそれがある。 However, since silver-plated material is soft and easily worn, when it is used as a material for connection terminals, it is likely to adhere and wear due to insertion and removal or sliding, and the surface is scraped when the connection terminal is inserted. There is a problem that the friction coefficient becomes high and the insertion force becomes high. In particular, when the silver plating material is used as a material for a connector that can be inserted and removed such as a wire harness, if the silver plating film is scraped by repeated insertion and removal to expose the base plating film and the substrate, the contact resistance increases and heat is generated. And may cause ignition.
このような問題を解消するため、銀めっき皮膜を厚くする方法や、銀めっき材の表面に潤滑剤を塗布する方法が知られている。 In order to solve such a problem, a method of thickening the silver plating film and a method of applying a lubricant to the surface of the silver plating material are known.
しかし、銀めっき皮膜を厚くすると、製造コストが高くなり、銀めっき材の表面に潤滑剤を塗布する場合は、潤滑剤の塗布工程が必要になり、生産性が低下して製造コストが高くなる。 However, if the silver plating film is thickened, the manufacturing cost becomes high, and when the lubricant is applied to the surface of the silver plating material, a step of applying the lubricant is required, the productivity is lowered, and the manufacturing cost is high. ..
また、銀めっき材の表面に潤滑剤を塗布する方法として、ベンゾトリアゾールなどの特定のインヒビターと、特定の脂肪酸からなる潤滑剤と、特定のアルキルリン酸エステルからなる乳化剤を含む表面処理液を銀めっき材に塗布する方法（例えば、特許文献１参照）や、トルエン、アセトン、トリクロロエタンまたは合成溶剤に脂肪酸を含む有機化合物を溶解した溶液中に、貴金属またはこれを主成分とする合金からなる表層を有する電気接点材料を浸漬して、脂肪酸を含む有機化合物からなる有機皮膜を表層の表面に形成する方法（例えば、特許文献２参照）が提案されている。 In addition, as a method of applying a lubricant to the surface of a silver plating material, a surface treatment liquid containing a specific inhibitor such as benzotriazole, a lubricant composed of a specific fatty acid, and an emulsifier composed of a specific alkyl phosphate ester is silver. A surface layer made of a noble metal or an alloy containing a noble metal as a main component is formed in a method of applying to a plating material (see, for example, Patent Document 1) or a solution in which an organic compound containing a fatty acid is dissolved in toluene, acetone, trichloroethane or a synthetic solvent. A method has been proposed in which an organic contact material having an electric contact material is immersed to form an organic film composed of an organic compound containing a fatty acid on the surface of a surface layer (see, for example, Patent Document 2).
しかし、特許文献１の方法のように、ベンゾトリアゾールなどのインヒビターと脂肪酸を混合した表面処理液を銀めっき材の表面に塗布すると、十分な耐摩耗性の銀めっき材を得ることができない。また、特許文献２の方法では、トルエンなどの有機溶剤を使用しているため、取扱いや環境負荷などの観点から、生産性が低下して、製造コストが高くなる。 However, when a surface treatment liquid in which an inhibitor such as benzotriazole and a fatty acid are mixed is applied to the surface of the silver plating material as in the method of Patent Document 1, a silver plating material having sufficient wear resistance cannot be obtained. Further, since the method of Patent Document 2 uses an organic solvent such as toluene, the productivity is lowered and the manufacturing cost is high from the viewpoint of handling and environmental load.
したがって、本発明は、このような従来の問題点に鑑み、耐摩耗性に優れた安価な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, an object of the present invention is to provide an inexpensive silver plating material having excellent wear resistance and a method for producing the same.
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、基材上に銀からなる表層を形成した後、この表層を１０〜５０ｇ／Ｌの脂肪酸を含む水エマルジョンに浸漬して、表層の表面に厚さ１０〜５０ｎｍの有機皮膜を形成することにより、耐摩耗性に優れた安価な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 diligent research to solve the above problems, the present inventors formed a surface layer made of silver on a substrate, and then immersed the surface layer in an aqueous emulsion containing 10 to 50 g / L of fatty acid. They have found that an inexpensive silver-plated material having excellent wear resistance can be produced by forming an organic film having a thickness of 10 to 50 nm on the surface of the surface layer, and have completed the present invention.
すなわち、本発明による銀めっき材の製造方法は、基材上に銀からなる表層を形成した後、この表層を１０〜５０ｇ／Ｌの脂肪酸を含む水エマルジョンに浸漬して、表層の表面に厚さ１０〜５０ｎｍの有機皮膜を形成することを特徴とする。 That is, in the method for producing a silver-plated material according to the present invention, after forming a surface layer made of silver on a base material, the surface layer is immersed in an aqueous emulsion containing 10 to 50 g / L of fatty acid to make the surface of the surface layer thick. It is characterized by forming an organic film having a diameter of 10 to 50 nm.
この銀めっき材の製造方法において、脂肪酸がステアリン酸であるのが好ましい。また、基材が銅または銅合金からなるのが好ましく、基材と表層の間に、銅または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 method for producing the silver plating material, the fatty acid is preferably stearic acid. Further, the base material is preferably made of copper or a copper alloy, and it is preferable that a base layer made of copper or nickel is formed between the base material and the surface layer.
また、本発明による銀めっき材は、基材上に銀からなる表層が形成され、この表層の表面に厚さ１０〜５０ｎｍの有機皮膜が形成された銀めっき材において、銀めっき材から２枚の試験片を切り出して、一方の試験片を平板状試験片とするとともに、他方の試験片をインデント加工（Ｒ＝１．５ｍｍ）してインデント付き試験片とし、このインデント付き試験片を荷重３Ｎで平板状試験片の表面に押し付けながら、摺動速度１００ｍｍ／分、摺動距離５ｍｍで５往復摺動させたときのそれぞれの往路の摺動距離２．５ｍｍの位置で水平方向にかかる力の平均値（Ｆ）を負荷荷重（Ｎ）で除して、μ＝Ｆ／Ｎから算出した摩擦係数が０．０５〜０．２であることを特徴とする。 Further, the silver-plated material according to the present invention is a silver-plated material in which a surface layer made of silver is formed on a base material and an organic film having a thickness of 10 to 50 nm is formed on the surface of the surface layer. The test piece is cut out to make one test piece into a flat plate-shaped test piece, and the other test piece is indented (R = 1.5 mm) to make an indented test piece, and this indented test piece is loaded with 3N. The force applied in the horizontal direction at the position of the sliding distance of 2.5 mm on each outbound route when sliding 5 reciprocations at a sliding speed of 100 mm / min and a sliding distance of 5 mm while pressing against the surface of the flat plate-shaped test piece. The coefficient of friction calculated from μ = F / N by dividing the average value (F) by the load (N) is 0.05 to 0.2.
この銀めっき材において、有機皮膜が脂肪酸を含むのが好ましく、脂肪酸がステアリン酸であるのが好ましい。基材が銅または銅合金からなるのが好ましく、基材と表層の間に、銅または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 this silver plating material, the organic film preferably contains a fatty acid, and the fatty acid is preferably stearic acid. The base material is preferably made of copper or a copper alloy, and a base layer made of copper or nickel is preferably formed between the base material and the surface layer.
さらに、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。 Further, the contact or terminal component according to the present invention is characterized in that the above silver-plated material is used as a material.
本発明によれば、耐摩耗性に優れた安価な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 an inexpensive silver-plated material having excellent wear resistance and a method for producing the same.
本発明による銀めっき材の製造方法の実施の形態では、基材上に銀からなる表層を形成した後、この表層を１０〜５０ｇ／Ｌ、好ましくは１５〜４５ｇ／Ｌの脂肪酸を含む水エマルジョンに浸漬して、表層の表面に厚さ１０〜５０ｎｍ、好ましくは１０〜３０ｎｍの有機皮膜を形成する。水エマルジョン中の脂肪酸の濃度が１０ｇ／Ｌより低いと、十分な厚さ（１０ｎｍ以上）の有機皮膜を形成することができなくなり、５０ｇ／Ｌより高いと、有機皮膜が（５０ｎｍより）厚くなり過ぎて接触抵抗が上昇するおそれがある。 In the embodiment of the method for producing a silver-plated material according to the present invention, after forming a surface layer made of silver on a substrate, the surface layer is a water emulsion containing 10 to 50 g / L, preferably 15 to 45 g / L of fatty acid. To form an organic film having a thickness of 10 to 50 nm, preferably 10 to 30 nm, on the surface of the surface layer. If the concentration of fatty acids in the water emulsion is lower than 10 g / L, it becomes impossible to form an organic film of sufficient thickness (10 nm or more), and if it is higher than 50 g / L, the organic film becomes thicker (more than 50 nm). There is a risk that the contact resistance will increase too much.
この銀めっき材の製造方法では、表層を形成する前に、（好ましくは銅または銅合金からなる）基材をアルカリ脱脂や電解脱脂などにより前処理し、酸洗により基材の表面を酸活性させるのが好ましい。また、表層を形成する前（または酸活性後で表層を形成する前）に、基材と表層の密着性を向上させるとともに基材の成分の拡散を防止するために、めっきによりＣｕまたはＮｉからなる下地層を形成し、その後、シアン浴などによるＡｇストライクめっきにより中間層を形成した後、シアン浴などによるＡｇめっきにより表層を形成してもよい。これらのめっきは、電気めっきでも無電解めっきでもよい。 In this method for producing a silver-plated material, a base material (preferably made of copper or a copper alloy) is pretreated by alkaline degreasing, electrolytic degreasing, or the like before forming a surface layer, and the surface of the base material is acid-activated by pickling. It is preferable to let it. In addition, before forming the surface layer (or before forming the surface layer after acid activity), from Cu or Ni by plating in order to improve the adhesion between the base material and the surface layer and prevent the diffusion of the components of the base material. The underlying layer may be formed, and then an intermediate layer may be formed by Ag strike plating with a cyan bath or the like, and then a surface layer may be formed by Ag plating with a cyan bath or the like. These platings may be electroplating or electroless plating.
銀からなる表層は、銀めっき皮膜などの層であり、銀めっき皮膜を形成する際にめっき液に添加される微量のセレンやアンチモンなどの添加物を含んでもよい。なお、銀からなる表層が厚過ぎると、銀の使用量が多くなって生産性の低下や製造コストの増大を招き、表層が薄過ぎると、基材（または下地）の成分の拡散により接触抵抗が上昇するおそれがあるため、表層の厚さは、０．１〜３０μｍであるのが好ましく、０．３〜１０μｍであるのがさらに好ましく、０．５〜７μｍであるのが最も好ましい。また、ＣｕまたはＮｉからなる下地層が厚過ぎると、銀めっき材の曲げ加工性が低下し、薄過ぎると、基材と表層の密着性を向上させるとともに基材の成分の拡散を防止する効果が十分でないため、下地層の厚さは、０．０５〜３μｍであるのが好ましく、０．１〜２μｍであるのがさらに好ましい。 The surface layer made of silver is a layer such as a silver plating film, and may contain a trace amount of additives such as selenium and antimony added to the plating solution when the silver plating film is formed. If the surface layer made of silver is too thick, the amount of silver used will increase, resulting in a decrease in productivity and an increase in manufacturing cost. If the surface layer is too thin, the contact resistance will be caused by the diffusion of the components of the base material (or base material). The thickness of the surface layer is preferably 0.1 to 30 μm, more preferably 0.3 to 10 μm, and most preferably 0.5 to 7 μm. Further, if the base layer made of Cu or Ni is too thick, the bending workability of the silver plating material is lowered, and if it is too thin, the adhesion between the base material and the surface layer is improved and the diffusion of the components of the base material is prevented. The thickness of the base layer is preferably 0.05 to 3 μm, more preferably 0.1 to 2 μm.
有機皮膜は、脂肪酸を含む皮膜であり、脂肪酸を含む水エマルジョン浴中に表層を浸漬することによって形成することができる。この脂肪酸として、ステアリン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ベヘン酸、セロチン酸、メリシン酸などの飽和脂肪酸や、ミリストレイン酸、パルミトレイン酸、オレイン酸、ネルボン酸、リノール酸、α−リノレン酸などの不飽和脂肪酸を使用することができるが、ステアリン酸を使用するのが好ましい。 The organic film is a film containing fatty acids and can be formed by immersing the surface layer in a water emulsion bath containing fatty acids. These fatty acids include saturated fatty acids such as stearic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, bechenic acid, cellotic acid, and melissic acid, myristoleic acid, palmitreic acid, oleic acid, nervonic acid, and linoleic acid. Although unsaturated fatty acids such as acid and α-linoleic acid can be used, stearic acid is preferably used.
また、本発明による銀めっき材の実施の形態では、基材上に銀からなる表層が形成され、この表層の表面に厚さ１０〜５０ｎｍ、好ましくは１０〜３０ｎｍの有機皮膜が形成された銀めっき材において、銀めっき材から２枚の試験片を切り出して、一方の試験片を平板状試験片（雄端子としての試験片）とするとともに、他方の試験片をインデント加工（Ｒ＝１．５ｍｍの半球状の打ち出し加工）してインデント付き試験片（雌端子としての試験片）とし、このインデント付き試験片を荷重３Ｎで平板状試験片の表面に押し付けながら、摺動速度１００ｍｍ／分、摺動距離５ｍｍで５往復摺動させたときのそれぞれの往路の摺動距離２．５ｍｍの位置で水平方向にかかる力の平均値（Ｆ）を負荷荷重（Ｎ）で除して、μ＝Ｆ／Ｎから算出した摩擦係数が０．０５〜０．２、好ましくは０．０５〜０．１５である。この銀めっき材において、基材が銅または銅合金からなるのが好ましく、基材と表層の間に、銅またはニッケルからなる下地層を形成するのが好ましい。 Further, in the embodiment of the silver-plated material according to the present invention, a surface layer made of silver is formed on the base material, and an organic film having a thickness of 10 to 50 nm, preferably 10 to 30 nm is formed on the surface of the surface layer. In the plating material, two test pieces are cut out from the silver plating material, one test piece is used as a flat plate-shaped test piece (test piece as a male terminal), and the other test piece is indented (R = 1. (5 mm hemispherical embossing) to make an indented test piece (test piece as a female terminal), and while pressing this indented test piece against the surface of the flat plate-shaped test piece with a load of 3 N, the sliding speed is 100 mm / min. The average value (F) of the force applied in the horizontal direction at the position of the sliding distance of 2.5 mm on each outbound route when sliding 5 reciprocations at a sliding distance of 5 mm is divided by the load (N), and μ = The coefficient of friction calculated from F / N is 0.05 to 0.2, preferably 0.05 to 0.15. In this silver-plated material, the base material is preferably made of copper or a copper alloy, and it is preferable to form a base layer made of copper or nickel between the base material and the surface layer.
また、上記のインデント付き試験片を荷重３Ｎで上記の平板状試験片の表面に押し付けながら、摺動速度１００ｍｍ／分、摺動距離５ｍｍで５０往復摺動させる摺動試験後に、基材の表面が露出しないのが好ましく、摺動試験後の摩耗量（摺動方向に略垂直な断面において摩耗した面積）が５０μｍ２以下であるのが好ましく、２０μｍ２以下であるのがさらに好ましい。 Further, after a sliding test in which the indented test piece is pressed against the surface of the flat plate-shaped test piece with a load of 3N and slid 50 times at a sliding speed of 100 mm / min and a sliding distance of 5 mm, the surface of the base material is subjected to the sliding test. Is not exposed, and the amount of wear after the sliding test (the area worn in the cross section substantially perpendicular to the sliding direction) is preferably 50 μm 2 or less, and more preferably 20 μm 2 or less.
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 material according to the present invention and the method for producing the same will be described in detail.
［実施例１］
まず、基材（被めっき材）として６７ｍｍ×５０ｍｍ ×０．３ｍｍの純銅板を用意し、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、水洗した後、３％硫酸中で１５秒間酸洗を行った。
[Example 1]
First, a pure copper plate of 67 mm × 50 mm × 0.3 mm is prepared as a base material (material to be plated), and the material to be plated and the SUS plate are put into an alkaline degreasing solution, the material to be plated is used as a cathode, and the SUS plate is used as an anode. , Electrolyzed at a voltage of 5 V for 30 seconds, washed with water, and then pickled in 3% sulfuric acid for 15 seconds.
次に、５４０ｇ／Ｌのスルファミン酸ニッケル四水和物と２５ｇ／Ｌの塩化ニッケルと３５ｇ／Ｌのホウ酸を含む水溶液からなるニッケルめっき液中において、被めっき材を陰極とし、ＳＫニッケル電極板（住友金属鉱山株式会社製の住友ＳＫニッケルからなる電極板）を陽極として、スターラにより５００ｒｐｍで撹拌しながら液温５５℃において電流密度５Ａ／ｄｍ２で８２秒間電気めっきを行って、下地めっき皮膜として厚さ１μｍのニッケルめっき皮膜を形成した後、水洗してニッケルめっき液を十分に洗い流した。 Next, in a nickel plating solution consisting of an aqueous solution containing 540 g / L nickel sulfamate tetrahydrate, 25 g / L nickel chloride, and 35 g / L boric acid, the material to be plated is used as a cathode, and an SK nickel electrode plate is used. as an anode (Sumitomo Metal Mining electrode plate made of Co., Ltd. Sumitomo SK nickel), performs stirring solution temperature 55 ° C. 82 seconds electroplating at a current density of 5A / dm 2 in at 500rpm by stirrer, undercoat plating film After forming a nickel plating film having a thickness of 1 μm, the nickel plating solution was thoroughly washed away by washing with water.
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秒間電気めっきを行って、銀ストライクめっき皮膜を形成した後、水洗して銀ストライクめっき液を十分に洗い流した。 Next, in a silver strike plating solution consisting of an aqueous solution containing 3 g / L of silver potassium cyanide and 90 g / L of potassium cyanide, the material to be plated is used as a cathode, the titanium electrode plate coated with platinum is used as an anode, and the stirrer is used at 500 rpm. Electroplating was performed at a current density of 2 A / dm 2 for 10 seconds with stirring to form a silver strike plating film, which was then washed with water to thoroughly wash away the silver strike plating solution.
次に、１７５ｇ／Ｌのシアン化銀カリウム（ＫＡｇ（ＣＮ）２）と９５ｇ／Ｌのシアン化カリウム（ＫＣＮ）と１０２ｍｇ／Ｌのセレノシアン酸カリウム（ＫＳｅＣＮ）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１８℃において電流密度５Ａ／ｄｍ２で銀めっき皮膜の厚さが３μｍになるように７８秒間電気めっき（銀めっき）を行い、水洗して銀めっき液を十分に洗い流して、銀めっき材を得た。 Next, in a silver plating solution consisting of an aqueous solution containing 175 g / L of potassium cyanide (KAg (CN) 2 ), 95 g / L of potassium cyanide (KCN), and 102 mg / L of potassium cyanide (KSeCN). Using the plating material as the cathode and the silver electrode plate as the anode, electroplating (silver) for 78 seconds so that the thickness of the silver plating film becomes 3 μm at a liquid temperature of 18 ° C. and a current density of 5 A / dm 2 while stirring with a stirrer at 500 rpm. Plating) was performed, and the mixture was washed with water to thoroughly wash away the silver plating solution to obtain a silver plating material.
次に、後処理として、１６ｇ／Ｌのステアリン酸を含む水エマルジョン浴中に銀めっき材をスターラにより５００ｒｐｍで撹拌しながら１０秒間浸漬した。その後、この銀めっき材の表面に対して、上から下に向かって口径７０ｍｍのドライヤーで１５ｍ／ｓの温風を当てて、表面の水分を完全に除去した後、加熱乾燥機（アズワン株式会社製のスチール強制対流乾燥機ＯＦ−４５０）により大気中において１１０℃で４５秒間加熱して乾燥させた（乾燥方法１）。 Next, as a post-treatment, the silver plating material was immersed in a water emulsion bath containing 16 g / L stearic acid for 10 seconds while stirring with a stirrer at 500 rpm. Then, the surface of this silver-plated material is blown with warm air of 15 m / s from top to bottom with a dryer having a diameter of 70 mm to completely remove the moisture on the surface, and then a heat dryer (AS ONE Corporation). The steel forced convection dryer OF-450) was heated in the air at 110 ° C. for 45 seconds to dry (drying method 1).
このようにして得られた後処理後の銀めっき材について、熱分解型ガスクロマトグラフ質量分析計により銀めっき皮膜の表面の定性分析を行ったところ、銀めっき皮膜の表面にステアリン酸を含む有機皮膜が確認された。また、アルゴンイオンを照射することにより銀めっき皮膜の表面（の直径１００μｍの分析エリア）をスパッタし、オージェ電子分光分析装置（日本電子株式会社製のＪＡＭＰ−７８００）を使用してオージェ電子分光法（ＡＥＳ）による深さプロファイル分析を行ったところ、銀めっき皮膜の表面に有機皮膜が付着しているのが確認された。この有機皮膜の厚さ（炭素を含む皮膜の厚さ）を、スパッタリング時間から、ＳｉＯ２の標準試料のスパッタリング速度（５ｎｍ／分）に換算して求めたところ、１２ｎｍであった。また、得られた銀めっき材を目視により観察したところ、外観ムラはなかった。 A qualitative analysis of the surface of the silver-plated film was performed on the post-treated silver-plated material thus obtained by a thermal decomposition type gas chromatograph mass spectrometer. As a result, the surface of the silver-plated film was an organic film containing stearic acid. Was confirmed. In addition, the surface of the silver plating film (analysis area with a diameter of 100 μm) is sputtered by irradiating with argon ions, and Auger electron spectroscopy using an Auger electron spectroscopy analyzer (JAMP-7800 manufactured by JEOL Ltd.) When the depth profile analysis by (AES) was performed, it was confirmed that the organic film was attached to the surface of the silver-plated film. The thickness of the organic film (thickness of the film containing carbon) was calculated by converting it from the sputtering time to the sputtering rate (5 nm / min) of the standard sample of SiO 2 , and it was 12 nm. Moreover, when the obtained silver-plated material was visually observed, there was no unevenness in appearance.
また、後処理後の銀めっき材から２枚の試験片を切り出して、一方の試験片を平板状試験片（雄端子としての試験片）とするとともに、他方の試験片をインデント加工（Ｒ＝１．５ｍｍの半球状の打ち出し加工）してインデント付き試験片（雌端子としての試験片）とし、摺動試験装置として精密摺動試験機（株式会社山崎精機研究所製のＣＲＳ−Ｇ２０５０−ＤＷＡ型）のステージに平板状試験片を固定し、その平板状試験片にインデント付き試験片を接触させた後、荷重３Ｎでインデント付き試験片を平板状試験片の表面に押し付けながら、平板状試験片を固定したステージを水平方向に摺動速度１００ｍｍ／分、摺動距離５ｍｍで５０往復摺動させる摺動試験を行った後、摩耗痕評価装置としてマイクロスコープ（株式会社キーエンス製のＶＫ−９７００）を使用し、倍率５００倍で平板状試験片の表面を観察して、基材（純銅板）の表面の露出の有無を観察したところ、基材の表面の露出はなかった。また、摺動試験後の平板状試験片の摺動痕の断面プロファイルから得られた摺動痕の面積から摩耗量（摺動方向に略垂直な断面において摩耗した面積）を算出したところ、摩耗量はほぼ０μｍ２であった。 In addition, two test pieces are cut out from the silver-plated material after the post-treatment, one test piece is used as a flat plate-shaped test piece (test piece as a male terminal), and the other test piece is indented (R =). 1.5 mm hemispherical embossing) to make an indented test piece (test piece as a female terminal), and a precision sliding tester (CRS-G2050-DWA manufactured by Yamasaki Seiki Laboratory Co., Ltd.) as a sliding test device. After fixing the flat plate-shaped test piece to the stage of the mold) and bringing the indented test piece into contact with the flat plate-shaped test piece, the flat plate-shaped test is performed while pressing the indented test piece against the surface of the flat plate-shaped test piece with a load of 3N. After conducting a sliding test in which a stage with a fixed piece is slid horizontally at a sliding speed of 100 mm / min and a sliding distance of 5 mm for 50 reciprocations, a microscope (VK-9700 manufactured by Keyence Co., Ltd.) was used as a wear mark evaluation device. ) Was used, and the surface of the flat plate-shaped test piece was observed at a magnification of 500 times to observe whether or not the surface of the base material (pure copper plate) was exposed. As a result, the surface of the base material was not exposed. Further, when the amount of wear (the area worn in the cross section substantially perpendicular to the sliding direction) was calculated from the area of the sliding marks obtained from the cross-sectional profile of the sliding marks of the flat plate-shaped test piece after the sliding test, the wear was found. The amount was approximately 0 μm 2 .
また、上記と同様の摺動試験を行い、５往復摺動させたときのそれぞれの往路の摺動距離２．５ｍｍの位置で水平方向にかかる力の平均値（Ｆ）を測定し、負荷荷重（Ｎ）で除して、μ＝Ｆ／Ｎから摩擦係数を算出したところ、摩擦係数は０．０９であった。 Further, a sliding test similar to the above is performed, and the average value (F) of the force applied in the horizontal direction is measured at a position where the sliding distance of each outward path is 2.5 mm when sliding 5 reciprocations, and the load is loaded. When the friction coefficient was calculated from μ = F / N by dividing by (N), the friction coefficient was 0.09.
［実施例２］
水エマルジョン浴中のステアリン酸の濃度を３１ｇ／Ｌとした以外は、実施例１と同様の方法により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、外観ムラの有無を観察し、摺動試験後の基材の表面の露出の有無を観察し、摩耗量および摩擦係数を算出したところ、外観ムラはなく、摺動試験後の基材の表面の露出はなく、摩耗量はほぼ０μｍ２であり、摩擦係数は０．０９であった。
[Example 2]
For the silver-plated material obtained by the same method as in Example 1 except that the concentration of stearic acid in the water emulsion bath was 31 g / L, the presence or absence of uneven appearance was observed by the same method as in Example 1. When the presence or absence of exposure of the surface of the base material after the sliding test was observed and the amount of wear and the coefficient of friction were calculated, there was no uneven appearance, the surface of the base material was not exposed after the sliding test, and the amount of wear was It was approximately 0 μm 2 and had a coefficient of friction of 0.09.
［実施例３］
水エマルジョン浴中の浸漬時間を１２０秒とし、浸漬後にドライヤーによる水分の除去と加熱乾燥を行う代わりに、孔径１．５ｍｍのエアガンで空気圧縮による水分除去（乾燥方法２）を行った以外は、実施例２と同様の方法により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、外観ムラの有無を観察し、摺動試験後の基材の表面の露出の有無を観察し、摩耗量および摩擦係数を算出したところ、外観ムラはあったが、摺動試験後の基材の表面の露出はなく、摩耗量は９μｍ２と少なく、摩擦係数は０．１０であった。
[Example 3]
The immersion time in the water emulsion bath was 120 seconds, and instead of removing the moisture with a dryer and heating and drying after immersion, the moisture was removed by air compression with an air gun having a pore size of 1.5 mm (drying method 2). With respect to the silver-plated material obtained by the same method as in Example 2, the presence or absence of appearance unevenness was observed by the same method as in Example 1, and the presence or absence of exposure of the surface of the base material after the sliding test was observed. When the amount of wear and the coefficient of friction were calculated, the appearance was uneven, but the surface of the base material was not exposed after the sliding test, the amount of wear was as small as 9 μm 2, and the coefficient of friction was 0.10.
［比較例１］
水エマルジョン浴中のステアリン酸の濃度を３．１ｇ／Ｌとした以外は、実施例１と同様の方法により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、有機皮膜の厚さを測定し、外観ムラの有無を観察し、摺動試験後の基材の表面の露出の有無を観察し、摩耗量および摩擦係数を算出したところ、有機皮膜の厚さは２．５ｎｍであり、外観ムラはなかったが、摺動試験後の基材の表面が露出し、摩耗量は１１４μｍ２と多く、摩擦係数は０．１０であった。
[Comparative Example 1]
With respect to the silver-plated material obtained by the same method as in Example 1 except that the concentration of stearic acid in the water emulsion bath was 3.1 g / L, the thickness of the organic film was increased by the same method as in Example 1. The thickness of the organic film was 2.5 nm when the amount of wear and the coefficient of friction were calculated by observing the presence or absence of appearance unevenness and observing the presence or absence of exposure of the surface of the base material after the sliding test. Although there was no unevenness in appearance, the surface of the base material after the sliding test was exposed, the amount of wear was as large as 114 μm 2, and the friction coefficient was 0.10.
［比較例２］
水エマルジョン浴中のステアリン酸の濃度を１．６ｇ／Ｌとした以外は、実施例１と同様の方法により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、有機皮膜の厚さを測定し、外観ムラの有無を観察し、摺動試験後の基材の表面の露出の有無を観察し、摩耗量および摩擦係数を算出したところ、有機皮膜の厚さは１．５ｎｍであり、外観ムラはなかったが、摺動試験後の基材の表面が露出し、摩耗量は３５０μｍ２と多く、摩擦係数は０．３６と高かった。
[Comparative Example 2]
With respect to the silver-plated material obtained by the same method as in Example 1 except that the concentration of stearic acid in the water emulsion bath was 1.6 g / L, the thickness of the organic film was increased by the same method as in Example 1. The thickness of the organic film was 1.5 nm when the amount of wear and the coefficient of friction were calculated by observing the presence or absence of appearance unevenness and observing the presence or absence of exposure of the surface of the base material after the sliding test. Although there was no unevenness in appearance, the surface of the base material after the sliding test was exposed, the amount of wear was as large as 350 μm 2, and the friction coefficient was as high as 0.36.
［比較例３］
水エマルジョン浴中のステアリン酸の濃度を０．８ｇ／Ｌとした以外は、実施例１と同様の方法により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、有機皮膜の厚さを測定し、外観ムラの有無を観察し、摺動試験後の基材の表面の露出の有無を観察し、摩耗量および摩擦係数を算出したところ、有機皮膜の厚さは１．２５ｎｍであり、外観ムラはなかったが、摺動試験後の基材の表面が露出し、摩耗量は１４８μｍ２と多く、摩擦係数は０．８２と高かった。
[Comparative Example 3]
For the silver-plated material obtained by the same method as in Example 1 except that the concentration of stearic acid in the water emulsion bath was 0.8 g / L, the thickness of the organic film was increased by the same method as in Example 1. Was measured, the presence or absence of appearance unevenness was observed, the presence or absence of exposure of the surface of the base material after the sliding test was observed, and the amount of wear and the coefficient of friction were calculated. As a result, the thickness of the organic film was 1.25 nm. Although there was no unevenness in appearance, the surface of the base material after the sliding test was exposed, the amount of wear was as large as 148 μm 2, and the friction coefficient was as high as 0.82.
［比較例４］
水エマルジョン浴中に被めっき材を浸漬した後、エアガンで空気圧縮による水分除去を行う前に水洗した以外は、実施例３と同様の方法により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、有機皮膜の厚さを測定し、外観ムラの有無を観察し、摺動試験後の基材の表面の露出の有無を観察し、摩耗量および摩擦係数を算出したところ、有機皮膜の厚さは１ｎｍ未満であり、外観ムラはなかったが、摺動試験後の基材の表面が露出し、摩耗量は８５８μｍ２と多く、摩擦係数は１．３８と高かった。
[Comparative Example 4]
The silver-plated material obtained by the same method as in Example 3 is the same as in Example 1 except that the material to be plated is immersed in a water emulsion bath and then washed with water before removing water by air compression with an air gun. The thickness of the organic film was measured by the method described in the above method, the presence or absence of uneven appearance was observed, the presence or absence of exposure of the surface of the base material after the sliding test was observed, and the amount of wear and the coefficient of friction were calculated. The thickness of the plating was less than 1 nm, and there was no uneven appearance, but the surface of the base material after the sliding test was exposed, the amount of wear was as large as 858 μm 2, and the friction coefficient was as high as 1.38.
［比較例５］
水エマルジョン浴中に浸漬する処理を行わなかった以外は、比較例４と同様の方法により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、有機皮膜の厚さを測定し、外観ムラの有無を観察し、摺動試験後の基材の表面の露出の有無を観察し、摩耗量および摩擦係数を算出したところ、有機皮膜の厚さは０ｎｍであり、外観ムラはなかったが、摺動試験後の基材の表面が露出し、摩耗量は２０６μｍ２と多く、摩擦係数は１．２３と高かった。
[Comparative Example 5]
With respect to the silver-plated material obtained by the same method as in Comparative Example 4 except that the treatment of immersing in the water emulsion bath was not performed, the thickness of the organic film was measured by the same method as in Example 1 and the appearance was measured. When the presence or absence of unevenness was observed, the presence or absence of exposure of the surface of the base material after the sliding test was observed, and the amount of wear and the coefficient of friction were calculated, the thickness of the organic film was 0 nm, and there was no uneven appearance. The surface of the base material after the sliding test was exposed, the amount of wear was as high as 206 μm 2, and the friction coefficient was as high as 1.23.
［比較例６］
ステアリン酸を含む水エマルジョン浴の代わりにチオール系化合物を含む浴を使用し、浸漬時間を１０秒とした以外は、比較例４と同様の方法により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、摺動試験後の基材の表面の露出の有無を観察し、摩耗量および摩擦係数を算出したところ、摺動試験後の基材の表面が露出し、摩耗量は２４２９μｍ２と多く、摩擦係数は１．１３と高かった。
[Comparative Example 6]
Examples 1 and the silver-plated material obtained by the same method as in Comparative Example 4 except that a bath containing a thiol compound was used instead of the water emulsion bath containing stearic acid and the immersion time was 10 seconds. When the presence or absence of exposure of the surface of the base material after the sliding test was observed by the same method and the amount of wear and the coefficient of friction were calculated, the surface of the base material after the sliding test was exposed and the amount of wear was 2429 μm 2. The coefficient of friction was as high as 1.13.
［比較例７］
ステアリン酸を含む水エマルジョン浴の代わりに４質量％のベンゾトリアゾールナトリウム（ＢＴＡ系化合物）を含む水溶液を使用し、浸漬時間を６０秒とした以外は、比較例５と同様の方法により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、摺動試験後の基材の表面の露出の有無を観察し、摩耗量および摩擦係数を算出したところ、摺動試験後の基材の表面が露出し、摩耗量は２０６８μｍ２と多く、摩擦係数は１．４９と高かった。
[Comparative Example 7]
It was obtained by the same method as in Comparative Example 5 except that an aqueous solution containing 4% by mass of benzotriazole sodium (BTA-based compound) was used instead of the water emulsion bath containing stearic acid and the immersion time was 60 seconds. For the silver-plated material, the presence or absence of exposure of the surface of the base material after the sliding test was observed by the same method as in Example 1, and the amount of wear and the coefficient of friction were calculated. As a result, the surface of the base material after the sliding test was calculated. Was exposed, the amount of wear was as high as 2068 μm 2, and the coefficient of friction was as high as 1.49.
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。 Tables 1 and 2 show the production conditions and characteristics of the silver-plated materials of these Examples and Comparative Examples.
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