JP5315571B2 - Stainless steel conductive member and manufacturing method thereof - Google Patents
Stainless steel conductive member and manufacturing method thereof Download PDFInfo
- Publication number
- JP5315571B2 JP5315571B2 JP2007119693A JP2007119693A JP5315571B2 JP 5315571 B2 JP5315571 B2 JP 5315571B2 JP 2007119693 A JP2007119693 A JP 2007119693A JP 2007119693 A JP2007119693 A JP 2007119693A JP 5315571 B2 JP5315571 B2 JP 5315571B2
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- conductive member
- lithium
- member according
- passive film
- 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.)
- Active
Links
- 239000010935 stainless steel Substances 0.000 title claims description 74
- 229910001220 stainless steel Inorganic materials 0.000 title claims description 74
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000011282 treatment Methods 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims description 14
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 claims description 10
- 238000002042 time-of-flight secondary ion mass spectrometry Methods 0.000 claims description 10
- 238000007654 immersion Methods 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 238000005554 pickling Methods 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 150000002500 ions Chemical group 0.000 claims description 5
- 229910000734 martensite Inorganic materials 0.000 claims description 5
- 229910000859 α-Fe Inorganic materials 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000004881 precipitation hardening Methods 0.000 claims 1
- 239000000463 material Substances 0.000 description 27
- 238000007747 plating Methods 0.000 description 18
- 238000005868 electrolysis reaction Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 14
- 238000005259 measurement Methods 0.000 description 11
- 239000010949 copper Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000005521 carbonaceous coating layer Substances 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 150000002642 lithium compounds Chemical group 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000010247 contact dermatitis Diseases 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Images
Landscapes
- Chemical Treatment Of Metals (AREA)
- Non-Insulated Conductors (AREA)
Description
本発明は、ステンレス鋼の表面意匠性、加工性、ばね特性および耐食性を維持しながら、接触電気抵抗を著しく改善したステンレス鋼製導電性部材およびその製造方法に関する。 The present invention relates to a stainless steel conductive member and a method for producing the same, in which the contact electrical resistance is remarkably improved while maintaining the surface designability, workability, spring characteristics and corrosion resistance of stainless steel.
従来、電子部品に使用されるスイッチ、リレー、コネクターなどの接点ばねや皿ばね（タクトスイッチ、マルチスイッチ）の基材には銅系合金が使用されていた。しかし、導電性部材の軽量化、薄肉化の要求およびばね特性が優れることから、銅系合金に代えてステンレス鋼が導電性材料の基材として広く使用されるようになってきた。 Conventionally, copper-based alloys have been used as the base material for contact springs and disc springs (tact switches, multi-switches) such as switches, relays, and connectors used in electronic components. However, since the requirements for weight reduction and thinning of the conductive member and the spring characteristics are excellent, stainless steel has been widely used as a base material for the conductive material in place of the copper-based alloy.
ステンレス鋼表面には、低い電気伝導性を示す不働態皮膜が存在し、これが接触電気抵抗を高くするため、電気接点機能が要求される部品にステンレス鋼部材を用いた場合には問題となる。この不働態皮膜は、酸洗や機械研磨によって除去しても、大気中では短時間に再生してしまう。このため、通常ステンレス鋼は、表面に生成している不働態皮膜を除去した後、その再生を防止しながら、密着性の優れる下地めっきを施し、その上層に電気伝導性が優れる錫-鉛（はんだ）、錫や貴金属の銀、金などがめっきされ、接触電気抵抗を改善した状態で使用される。また、金属めっき以外では、カーボン質被覆層で優れた電気伝導性が付与されたステンレス鋼（特許文献１）や、Cuリッチ層の析出又はCu濃化層を表層に形成したステンレス鋼（特許文献２）が知られている。 A passive film showing low electrical conductivity exists on the surface of stainless steel, and this increases the contact electrical resistance, which causes a problem when a stainless steel member is used for a component requiring an electrical contact function. Even if this passive film is removed by pickling or mechanical polishing, it is regenerated in the air in a short time. For this reason, after removing the passive film formed on the surface, stainless steel is usually coated with an undercoating with excellent adhesion while preventing its regeneration, and tin-lead ( Solder), tin, precious metals such as silver and gold are plated and used in a state where contact electric resistance is improved. In addition to metal plating, stainless steel (Patent Document 1) to which excellent electrical conductivity is imparted by a carbonaceous coating layer, and stainless steel having a Cu rich layer deposited or Cu concentrated layer formed on the surface layer (Patent Document 1) 2) is known.
上述のごとく、ステンレス鋼を電気接点部品の基材として使用する場合、電気伝導性が優れる錫-鉛（はんだ）、錫、銀、金などをステンレス鋼表面にめっきして接触電気抵抗を改善する必要がある。しかしながら、錫ではめっき処理時にウイスカー（ひげ状結晶）が発生し易く、このウイスカー発生を防止できる鉛-錫合金めっきでは、鉛の排液処理が問題となる。また、銀めっきでは、部品として組み込んだ後、イオンマイグレーション（ion migration）が発生し易く、接触不良や絶縁破壊を起こす可能性がある。さらに金では、めっき液にシアンを用いることが多いため、鉛と同様に排液処理が問題となり、製造プロセスとして環境的に好ましくない。 As mentioned above, when stainless steel is used as the base material for electrical contact parts, the electrical resistance is improved by plating the surface of the stainless steel with tin-lead (solder), tin, silver, gold, etc., which has excellent electrical conductivity. There is a need. However, in tin, whiskers (whisker-like crystals) are likely to occur during the plating process, and in the lead-tin alloy plating that can prevent the generation of whiskers, the draining process of lead becomes a problem. In addition, in silver plating, after being incorporated as a part, ion migration is likely to occur, and there is a possibility of causing contact failure or dielectric breakdown. Further, since gold often uses cyan as a plating solution, drainage treatment becomes a problem as in the case of lead, which is not environmentally preferable as a manufacturing process.
なお、金めっきでは0.5μm程度のめっき厚さで使用されることが多いが、めっき皮膜には欠陥が多く存在し、腐食性の強い環境で使用される場合には、金が下地金属の溶出を促進する。これを防止するために、めっき厚さを3μm以上にして皮膜の欠陥を少なくする対策もあるが、製造コストを上昇させる原因となる。
また通常、電気接点ばね部品は、ステンレス鋼の板材やコイル材にめっきした後、プレス打ち抜き成型によって対象部品に加工される。しかしながら、めっき皮膜には内部応力が存在し、これが原因となり、プレス成型後に反りなどが発生して要求される形状が得られないことがある。導電性部材の軽量化、薄肉化の要求が高まれば高まるほど、基材の板厚は薄くなり、このめっき皮膜の内部応力の影響が大きくなる。
Gold plating is often used with a plating thickness of about 0.5μm, but the plating film has many defects, and when used in a highly corrosive environment, gold is eluted from the base metal. Promote. In order to prevent this, there is a measure to reduce the defects of the film by increasing the plating thickness to 3 μm or more, but this causes an increase in manufacturing cost.
In general, the electrical contact spring component is processed into a target component by press punching after plating on a stainless steel plate or coil material. However, there is an internal stress in the plating film, which causes a warp after press molding, and the required shape may not be obtained. As the demand for lighter and thinner conductive members increases, the thickness of the base material becomes thinner, and the influence of the internal stress of the plating film increases.
さらに、カーボン質被覆層で優れた電気伝導性が付与されたステンレス鋼では、多数のピット表面が形成されたステンレス鋼板を基材とし、カーボン質被覆層が基材表面に設けられている（特許文献１）。ピットによるアンカー効果および実効表面積が大きくなることによって、ステンレス鋼基材とカーボン質被覆層は優れた密着性を呈するとされているが、プレス成型などの加工にカーボン質被覆層が追従できるとは考えられず、とくに、浅いピット部ではアンカー効果は低く、密着性、耐久性に問題があると考えられる。 Furthermore, in stainless steel to which excellent electrical conductivity is imparted by the carbonaceous coating layer, a stainless steel plate having a large number of pit surfaces is used as a base material, and the carbonaceous coating layer is provided on the base material surface (patent) Reference 1). Stainless steel substrate and carbonaceous coating layer are said to exhibit excellent adhesion due to the increased anchor effect and effective surface area due to pits, but the carbonaceous coating layer can follow press molding and other processing It is unthinkable, especially in shallow pits, the anchor effect is low, and it is considered that there are problems in adhesion and durability.
Cuリッチ層の析出又はCu濃化層を表層に形成したステンレス鋼（特許文献２）では、Cuの析出熱処理に長時間を要し、製造コストの上昇や、Cuを基材に含有しないSUS304鋼などの汎用鋼では処理が不可能など、問題点も多い。 Stainless steel with a Cu-rich layer precipitation or Cu-enriched layer formed on the surface (Patent Document 2) requires a long time for Cu precipitation heat treatment, resulting in increased manufacturing costs and SUS304 steel that does not contain Cu as a base material. There are many problems, such as being impossible to process with general-purpose steel.
従って、本発明の目的は、外観状ステンレス鋼表面が有する意匠性を保持したまま、ステンレス鋼表面の不働態皮膜を改質して、導電性が優れ、低い接触電気抵抗を有するステンレス鋼製導電性部材を提供することである。
本発明の他の目的は、外観状ステンレス鋼表面が有する意匠性を保持したまま、ステンレス鋼表面の不働態皮膜を改質して、導電性が優れ、低い接触電気抵抗を有するステンレス鋼製導電性部材の製造方法を提供することである。
本発明のさらに他の目的は、処理液の排液処理の問題が少なく、部品として組み込んだ後、めっき皮膜に起因するイオンマイグレーション、接触不良、絶縁破壊を起こす可能性が低く、製造コストが低く、加工の際に生じる内部応力が少ないステンレス鋼製導電性部材の製造方法を提供することである。
Therefore, the object of the present invention is to modify the passive film on the surface of the stainless steel while maintaining the design properties of the appearance-like stainless steel surface, and to make a stainless steel conductive material having excellent conductivity and low contact electric resistance. Providing a sex member.
Another object of the present invention is to improve the passive film on the surface of the stainless steel while maintaining the design properties of the appearance of the stainless steel surface, and to provide a stainless steel conductive material having excellent conductivity and low contact electric resistance. It is providing the manufacturing method of a sex member.
Still another object of the present invention is that there are few problems with the treatment liquid drainage treatment, and it is less likely to cause ion migration, poor contact, or dielectric breakdown due to the plating film after being assembled as a part, and the manufacturing cost is low. Another object of the present invention is to provide a method for producing a stainless steel conductive member that generates less internal stress during processing.
本発明は、ステンレス鋼表面不働態皮膜にリチウムイオンを化学的または電気化学的に注入し、不働態皮膜の電気伝導性を向上させたステンレス鋼製導電性部材を提供するものである。
本発明はまた、ステンレス鋼表面不働態皮膜にリチウムイオンを化学的または電気化学的に注入し、不働態皮膜の電気伝導性を向上させたステンレス鋼製導電性部材の製造方法を提供するものである。
本発明は以下に示すステンレス鋼製導電性部材およびその製造方法を提供するものである。
１．ステンレス鋼製導電性部材において、不働態皮膜中に０．０１原子％以上のリチウムを含有することを特徴とするステンレス鋼製導電性部材。
２．不働態皮膜中に０．０２原子％以上のリチウムを含有する上記１記載のステンレス鋼製導電性部材。
３．飛行時間型二次イオン質量分析（ToF-SIMS）による不働態皮膜中のCr酸化物水酸化物の二次イオン強度のピーク位置が、Fe酸化物水酸化物の二次イオン強度のピーク位置より深部にあることを特徴とする上記１または２記載のステンレス鋼製導電性部材。
４．ステンレス鋼が、オーステナイト系、フェライト系、マルテンサイト系、オーステナイト・フェライト（2相）、または析出硬化系ステンレス鋼である上記１〜３のいずれか１項記載のステンレス鋼製導電性部材。
５．ステンレス鋼が、SUS301、SUS304、SUS316、SUS430、SUS430J1L、SUS434、SUS444、またはSUS631である上記１〜３のいずれか１項記載のステンレス鋼製導電性部材。
６．ステンレス鋼が、光輝焼鈍仕上げ（BA）、酸洗仕上げ（2D）、酸洗後軽圧延仕上げ（2B）、または調質圧延仕上げ鋼である上記１〜５のいずれか１項記載のステンレス鋼製導電性部材。
７．リチウムイオンを含有する水溶液または非水溶液中でステンレス鋼をカソード電解処理または浸漬処理することを特徴とするステンレス鋼製導電性部材の製造方法。
８．リチウムイオン源が、水酸化リチウム、酸化リチウム、塩化リチウム、臭化リチウム、ヨウ化リチウム、硝酸リチウム、および硫酸リチウムからなる群から選ばれる少なくとも１種である上記７記載のステンレス鋼製導電性部材の製造方法。
９．カソード電解処理または浸漬処理後、大気中または不活性ガス雰囲気中において熱処理する工程を含む上記７または８記載のステンレス鋼製導電性部材の製造方法。
１０．ステンレス鋼が、オーステナイト系、フェライト系、マルテンサイト系、オーステナイト・フェライト（2相）、または析出硬化系ステンレス鋼である上記７〜９のいずれか１項記載のステンレス鋼製導電性部材の製造方法。
１１．ステンレス鋼が、SUS301、SUS304、SUS316、SUS430、SUS430J1L、SUS434、SUS444、またはSUS631である上記７〜９のいずれか１項記載のステンレス鋼製導電性部材の製造方法。
The present invention provides a stainless steel conductive member in which lithium ions are chemically or electrochemically injected into a stainless steel surface passive film to improve the electrical conductivity of the passive film.
The present invention also provides a method for producing a stainless steel conductive member in which lithium ions are chemically or electrochemically injected into a stainless steel surface passive film to improve the electrical conductivity of the passive film. is there.
The present invention provides the following stainless steel conductive member and method for producing the same.
1. A stainless steel conductive member, wherein the passive film contains 0.01 atomic% or more of lithium.
2. 2. The stainless steel conductive member as described in 1 above, wherein the passive film contains 0.02 atomic% or more of lithium.
3. The peak position of secondary ion intensity of Cr oxide hydroxide in the passive film by time-of-flight secondary ion mass spectrometry (ToF-SIMS) 3. The stainless steel conductive member according to 1 or 2 above, which is in a deep part.
4). 4. The stainless steel conductive member according to any one of 1 to 3 above, wherein the stainless steel is austenitic, ferritic, martensitic, austenitic ferrite (two-phase), or precipitation hardened stainless steel.
5. The stainless steel conductive member according to any one of the above items 1 to 3, wherein the stainless steel is SUS301, SUS304, SUS316, SUS430, SUS430J1L, SUS434, SUS444, or SUS631.
6). The stainless steel according to any one of 1 to 5 above, wherein the stainless steel is bright annealing finish (BA), pickling finish (2D), light rolling finish after pickling (2B), or temper rolled finish steel. Conductive member.
7). A method for producing a conductive member made of stainless steel, comprising subjecting stainless steel to cathodic electrolysis treatment or immersion treatment in an aqueous solution or non-aqueous solution containing lithium ions.
8). 8. The stainless steel conductive member according to 7 above, wherein the lithium ion source is at least one selected from the group consisting of lithium hydroxide, lithium oxide, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, and lithium sulfate. Manufacturing method.
9. 9. The method for producing a stainless steel conductive member according to 7 or 8, comprising a step of heat treatment in the air or in an inert gas atmosphere after the cathode electrolytic treatment or the immersion treatment.
10. The method for producing a stainless steel conductive member according to any one of 7 to 9 above, wherein the stainless steel is austenitic, ferritic, martensitic, austenitic ferrite (two-phase), or precipitation hardened stainless steel. .
11. The method for producing a stainless steel conductive member according to any one of 7 to 9 above, wherein the stainless steel is SUS301, SUS304, SUS316, SUS430, SUS430J1L, SUS434, SUS444, or SUS631.
本発明のステンレス鋼導電性部材は、導電性に優れ、低い接触電気抵抗を示し、高い接触感度を有する。また、本発明によれば、元来のステンレス鋼表面仕上げ状態を変化させることが外観上なく、めっき処理のような排液処理の問題が少なく、部品として組み込んだ後、イオンマイグレーション（ion migration）が発生せず、接触不良や絶縁破壊を起こす可能性が低く、製造コストが低いステンレス鋼製導電性部材を提供することができる。 The stainless steel conductive member of the present invention is excellent in conductivity, exhibits low contact electric resistance, and has high contact sensitivity. In addition, according to the present invention, the original surface finish state of stainless steel is not changed in appearance, and there are few problems of drainage treatment such as plating treatment. Therefore, it is possible to provide a stainless steel conductive member that has a low possibility of causing contact failure and dielectric breakdown, and has a low manufacturing cost.
本発明に使用されるステンレス鋼とは、オーステナイト系、フェライト系、マルテンサイト系、オーステナイト・フェライト（2相）、析出硬化系ステンレス鋼等を意味し、その具体例としては、SUS301、SUS304、SUS316、SUS430、SUS430J1L、SUS434、SUS444、SUS631等が挙げられる。また、表面仕上げ状態は、光輝焼鈍仕上げ（BA）、酸洗仕上げ（2D）、酸洗後軽圧延仕上げ（2B）、調質圧延仕上げ等が挙げられる。 The stainless steel used in the present invention means austenitic, ferritic, martensitic, austenitic ferrite (dual phase), precipitation hardened stainless steel, etc., and specific examples include SUS301, SUS304, SUS316. SUS430, SUS430J1L, SUS434, SUS444, SUS631, and the like. Surface finish conditions include bright annealing finish (BA), pickling finish (2D), light rolling finish after pickling (2B), temper rolling finish, and the like.
本発明のステンレス鋼製導電性部材は、例えば、リチウムイオンを含有する水溶液または非水溶液中でステンレス鋼をカソード電解処理（電気化学的処理）するか浸漬処理（化学的処理）することにより製造することができる。これらの処理によって、溶液中のリチウムイオンが不働態皮膜中へ進入する。電子のキャリアとなるLiが不働態皮膜の電気伝導性を向上させ、元来生成している不働態皮膜の接触電気抵抗を改善することが可能となる。 The stainless steel conductive member of the present invention is produced, for example, by subjecting stainless steel to cathode electrolytic treatment (electrochemical treatment) or immersion treatment (chemical treatment) in an aqueous solution or non-aqueous solution containing lithium ions. be able to. By these treatments, lithium ions in the solution enter the passive film. Li, which is an electron carrier, improves the electrical conductivity of the passive film, and improves the contact electrical resistance of the passive film that is originally formed.
さらに、リチウムイオンを不働態皮膜に注入させた後、大気中または不活性ガス雰囲気中で熱処理することによって、不働態皮膜の電気伝導性はさらに向上し、元来生成している不働態皮膜の接触電気抵抗を著しく改善することが可能となる。 Furthermore, by injecting lithium ions into the passive film and then heat-treating it in the air or in an inert gas atmosphere, the electrical conductivity of the passive film is further improved. The contact electrical resistance can be remarkably improved.
リチウムイオン源としては、水や非水溶媒に溶解して、リチウムイオンを生成するリチウム化合物であれば任意の化合物が使用できる。例えば、酸素化合物としては、水酸化リチウム、酸化リチウムなど、ハロゲン化物としては、塩化リチウム、臭化リチウム、ヨウ化リチウムなど、酸素酸塩としては、硝酸リチウム、硫酸リチウム、等が挙げられる。非水溶媒としては、エタノール、メタノール、エーテル（ジメチルエーテル、ジエチルエーテル、メチルエチルエーテル等具体的に記載して下さい。）等が挙げられる。水と水混和性非水溶媒の混合液も使用できる。 As the lithium ion source, any compound can be used as long as it is a lithium compound that dissolves in water or a non-aqueous solvent to generate lithium ions. For example, examples of the oxygen compound include lithium hydroxide and lithium oxide, examples of the halide include lithium chloride, lithium bromide, and lithium iodide. Examples of the oxyacid salt include lithium nitrate and lithium sulfate. Examples of the non-aqueous solvent include ethanol, methanol, ether (please specify dimethyl ether, diethyl ether, methyl ethyl ether, etc.). A mixture of water and a water-miscible non-aqueous solvent can also be used.
リチウムイオン源を含む水溶液または非水溶液中のリチウム化合物の濃度は、好ましくは0.1kmol・m-3以上であり、飽和溶液まで適する。溶液は加温する必要は無く、好ましくは１０〜３０℃、例えば、室温でよい。浸漬処理の場合、処理時間は好ましくは10秒間から10分間、さらに好ましくは３０秒間〜５分間程度が適する。カソード電解処理の場合、電流密度は好ましくは0.01A/dm2から10A/dm2、さらに好ましくは０．１〜５A/dm2、電解時間は好ましくは10秒間から10分間、さらに好ましくは２０秒間〜５分間程度が適する。 The concentration of the lithium compound in the aqueous solution or non-aqueous solution containing the lithium ion source is preferably 0.1 kmol · m −3 or more, and is suitable up to a saturated solution. The solution does not need to be heated and is preferably 10 to 30 ° C., for example, room temperature. In the case of immersion treatment, the treatment time is preferably 10 seconds to 10 minutes, more preferably about 30 seconds to 5 minutes. In the case of cathodic electrolysis, the current density is preferably 0.01 A / dm 2 to 10 A / dm 2 , more preferably 0.1 to 5 A / dm 2 , and the electrolysis time is preferably 10 seconds to 10 minutes, more preferably 20 seconds. About 5 minutes is suitable.
不働態皮膜にリチウムイオンを注入後、不働態皮膜の電気伝導性をさらに向上させるには、大気中、または窒素ガスやArなどの不活性ガス雰囲気中において熱処理することが望ましい。好適な熱処理温度は100℃〜300℃、さらに好ましくは１２０〜２３０℃であり、処理時間は好ましくは1分間から30分間、さらに好ましくは５〜２０分間である。 In order to further improve the electrical conductivity of the passive film after injecting lithium ions into the passive film, it is desirable to perform heat treatment in the air or in an inert gas atmosphere such as nitrogen gas or Ar. A suitable heat treatment temperature is 100 ° C. to 300 ° C., more preferably 120 to 230 ° C., and the treatment time is preferably 1 minute to 30 minutes, more preferably 5 to 20 minutes.
以下実施例を示し、本発明をさらに具体的に説明する。
実施例1
供試材
供試材には板厚が0.2mmのSUS304BA（BA：光輝焼鈍材）を使用した。これを15mm×50mmに切断して試験片とした。
Hereinafter, the present invention will be described more specifically with reference to examples.
Example 1
Test material SUS304BA (BA: bright annealing material) having a thickness of 0.2 mm was used as the test material. This was cut into 15 mm × 50 mm to obtain test pieces.
接触電気抵抗測定方法
接触電気抵抗は、株式会社 山崎精機研究所製、電気接点シミュレーター（CRS-113-金型）を使用して測定した。測定プローブには、PU-05金線接触子、0.5mmΦを用いた。印加定電流を10mAとした。また、接触子の最大接触荷重を100gf、移動距離を1mmとして測定を行い、接触荷重-接触電気抵抗分布曲線を求めた。
Contact electrical resistance measurement method Contact electrical resistance was measured using an electrical contact simulator (CRS-113-mold) manufactured by Yamazaki Seiki Laboratory Co., Ltd. The measurement probe used was a PU-05 gold wire contactor, 0.5 mmΦ. The applied constant current was 10 mA. The contact load was measured with a maximum contact load of 100 gf and a moving distance of 1 mm, and a contact load-contact electric resistance distribution curve was obtained.
実験方法
試験片をアセトン中に浸漬して超音波洗浄を施した後、1kmol・m-3LiOH水溶液中で1A/dm2で1分間のカソード電解を行い、蒸留水洗浄〜冷風（２５℃）乾燥を行なった後、100℃および200℃で10分間の大気加熱を行なった。また比較例として、SUS304BAに半光沢Niめっきした試験片の接触電気抵抗を測定した。
結果
図1に素材（SUS304BA：光輝焼鈍仕上げ）の接触荷重-接触電気抵抗分布曲線を示す。素材では、瞬間的に接触電気抵抗が低下する挙動は認められるものの、接触荷重が100gfまで、接触電気抵抗は300mΩ以上を保持したままである。
図2に、LiOH水溶液中でカソード電解後、大気加熱処理した試験片の接触荷重-接触電気抵抗分布曲線を示す。素材の接触電気抵抗はLi注入および、その後の100℃大気加熱によって低下し、さらに200℃での大気加熱を行なうことによって急激に低下した。また、200℃で大気加熱処理した試験片の接触電気抵抗は、図3に示す半光沢Niめっき材とほぼ同等になることがわかった。
Experimental method After immersing the test piece in acetone and subjecting it to ultrasonic cleaning, cathodic electrolysis at 1 A / dm 2 in 1 kmol · m -3 LiOH aqueous solution for 1 minute, distilled water cleaning to cold air (25 ° C) After drying, atmospheric heating was performed at 100 ° C. and 200 ° C. for 10 minutes. As a comparative example, the contact electric resistance of a test piece obtained by plating semi-gloss Ni onto SUS304BA was measured.
Results Figure 1 shows the contact load-contact resistance distribution curve of the material (SUS304BA: bright annealed finish). In the material, although the behavior that the contact electrical resistance decreases instantaneously is recognized, the contact electrical resistance remains at 300 mΩ or more up to a contact load of 100 gf.
FIG. 2 shows a contact load-contact electric resistance distribution curve of a test piece subjected to cathodic electrolysis in a LiOH aqueous solution and then subjected to atmospheric heat treatment. The contact electrical resistance of the material was lowered by Li injection and subsequent heating at 100 ° C., and then abruptly decreased by performing atmospheric heating at 200 ° C. Further, it was found that the contact electrical resistance of the test piece heated to the atmosphere at 200 ° C. was almost the same as that of the semi-bright Ni plating material shown in FIG.
素材BA皮膜、リチウム電解注入後、および200℃で大気加熱処理した皮膜の組成解析を飛行時間型二次イオン質量分析（ToF-SIMS）で行なった。皮膜の深さ方向の濃度分布は、皮膜をスパッタリングしながら、二次イオン強度の測定から求めた。測定結果を図4に示す。
カソード電解後に素材のBA皮膜内にLiの存在が認められた。さらに、200℃大気加熱処理後では、不働態皮膜の外層にLi、Feが存在し、内層にCrが存在することがわかった。
The composition analysis of the material BA film, the lithium electrolytic injection, and the film heat-treated at 200 ° C. was performed by time-of-flight secondary ion mass spectrometry (ToF-SIMS). The concentration distribution in the depth direction of the film was obtained by measuring the secondary ion intensity while sputtering the film. The measurement results are shown in FIG.
After cathode electrolysis, the presence of Li was observed in the BA film of the material. Furthermore, it was found that after atmospheric heat treatment at 200 ° C, Li and Fe were present in the outer layer of the passive film and Cr was present in the inner layer.
このようにして得られる本発明のステンレス鋼製導電性部材は、飛行時間型二次イオン質量分析（ToF-SIMS）で分析すると不働態被膜中に０．０１原子％以上、好ましくは０．０２原子％以上のＬｉを含んでおり、また下記の接触電気抵抗測定方法により測定した接触電気抵抗は、接触荷重５０gfにおいて、好ましくは１５０ｍΩ以下、さらに好ましくは１００ｍΩ以下である。 The thus obtained stainless steel conductive member of the present invention is analyzed by time-of-flight secondary ion mass spectrometry (ToF-SIMS), and is 0.01% by atom or more, preferably 0.02% in the passive film. The contact electrical resistance which contains atomic% or more of Li and measured by the following contact electrical resistance measurement method is preferably 150 mΩ or less, more preferably 100 mΩ or less at a contact load of 50 gf.
実施例2
供試材
実施例1に使用したものと同じ。
実験方法
接触電気抵抗に及ぼすリチウムイオンの最適濃度および最適温度の影響を調べるため、LiOH濃度を0.5から2kmol・m-3、水溶液温度を30、50、70℃として、1A/dm2で10分間のカソード電解処理を行なった。その後、蒸留水洗浄〜冷風乾燥し、200℃で10分間の大気加熱を施した。この試験片の接触荷重-接触電気抵抗分布曲線を測定して、接触電気抵抗が300mΩ以下に低下する接触荷重（低下荷重：gf）を求めた。測定回数、n=3で測定し、その平均値を表1に表わす。LiOH濃度が高くなるほど、低下荷重が小さくなる傾向が認められたが、水溶液温度の影響はなかった。
Example 2
Specimen Same as used in Example 1.
Experimental method To investigate the effect of the optimum concentration and temperature of lithium ions on the contact electrical resistance, LiOH concentration was 0.5 to 2 kmol · m -3 , aqueous solution temperature was 30, 50 and 70 ° C, 10 minutes at 1A / dm 2 The cathode electrolytic treatment was performed. Thereafter, it was washed with distilled water and dried with cold air, followed by heating at 200 ° C. for 10 minutes. The contact load-contact electric resistance distribution curve of this test piece was measured, and the contact load (decrease load: gf) at which the contact electric resistance decreased to 300 mΩ or less was determined. The number of measurements was measured at n = 3, and the average value is shown in Table 1. Although the decreasing load tended to decrease as the LiOH concentration increased, there was no effect of the aqueous solution temperature.
実施例3
供試材
実施例1に使用したものと同じ。
実験方法
接触電気抵抗に及ぼすカソード電流密度と、カソード電解後の加熱時間の影響を調べた。LiOH濃度を2kmol・m-3、水溶液温度を30℃、カソード電流密度を0.5から5A/dm2として、1分間のカソード電解後、200℃の大気中で5、10、30分間加熱した。測定回数、n=3で測定し、その平均値を求めた。表2に示すように、低下荷重に及ぼすカソード電流密度の影響は認められなかったが、最適大気加熱時間が10分間であることがわかった。また、LiOH水溶液中への浸漬処理のみでも接触電気抵抗を低下させる効果があることがわかった。
Example 3
Specimen Same as used in Example 1.
Experimental Method The influence of the cathode current density and the heating time after cathode electrolysis on the contact electrical resistance was investigated. The LiOH concentration was 2 kmol · m −3 , the aqueous solution temperature was 30 ° C., the cathode current density was 0.5 to 5 A / dm 2 , and the cathode electrolysis for 1 minute was followed by heating in the atmosphere at 200 ° C. for 5, 10 and 30 minutes. The number of measurements was measured at n = 3, and the average value was obtained. As shown in Table 2, the influence of the cathode current density on the drop load was not observed, but the optimum atmospheric heating time was found to be 10 minutes. Moreover, it was found that the contact electrical resistance was reduced only by the immersion treatment in the LiOH aqueous solution.
実施例4
供試材
実施例1に使用したものと同じ。
実験方法
接触電気抵抗に及ぼすカソード電解時間の影響を調べる目的で、LiOH濃度を2kmol・m-3、水溶液温度を30℃、カソード電流密度を1A/dm2として、電解時間を10秒間から5分間と変化させた。また、大気加熱処理は200℃で5、10、30分間とした。測定回数、n=3で測定し、その平均値を求めた。表3に示すように、低下荷重に及ぼすカソード電解時間の影響は認められなかったが、実施例3と同様に大気加熱時間は10分間が適していた。
Example 4
Specimen Same as used in Example 1.
In order to examine the effect of cathode electrolysis time on the experimental method the electrical contact resistance, LiOH concentration 2kmol · m -3, a solution temperature of 30 ° C., a cathode current density of 1A /
実施例5
供試材
実施例1に使用したものと同じ。
実験方法
接触電気抵抗に及ぼす大気加熱温度の影響を調べるため、LiOH濃度を2kmol・m-3、水溶液温度を30℃、カソード電解条件を1A/dm2で1分間とした。大気加熱温度を160℃から240℃まで変化させ、加熱時間は10分間とした。測定回数、n=3で測定し、その平均値を求めた。表4に示すように、200℃での大気加熱によって低下荷重が小さくなることがわかった。
Example 5
Specimen Same as used in Example 1.
Experimental Method In order to investigate the effect of atmospheric heating temperature on the contact electrical resistance, the LiOH concentration was 2 kmol · m −3 , the aqueous solution temperature was 30 ° C., and the cathode electrolysis conditions were 1 A / dm 2 for 1 minute. The atmospheric heating temperature was changed from 160 ° C. to 240 ° C., and the heating time was 10 minutes. The number of measurements was measured at n = 3, and the average value was obtained. As shown in Table 4, it was found that the drop load was reduced by atmospheric heating at 200 ° C.
実施例6
供試材
実施例1に使用したものと同じ。
実験方法
エタノールにLiNO3を溶解して、濃度を1kmol・m-3とした。この非水溶液中において、30℃、10Vで1分間のカソード電解を施し、その後、蒸留水洗浄〜冷風乾燥を行なった後、大気中で200℃×10分間の熱処理を行なった。接触荷重-接触電気抵抗分布曲線を図5に示す。
このように接触電気抵抗が低下することから、非水溶液からでもLiが不働態皮膜に注入できることがわかる。
Example 6
Specimen Same as used in Example 1.
Experimental Method LiNO 3 was dissolved in ethanol to a concentration of 1 kmol · m −3 . In this non-aqueous solution, cathode electrolysis was performed at 30 ° C. and 10 V for 1 minute, followed by washing with distilled water and cold air drying, followed by heat treatment at 200 ° C. for 10 minutes in the atmosphere. A contact load-contact electric resistance distribution curve is shown in FIG.
Since the contact electrical resistance is thus reduced, it can be seen that Li can be injected into the passive film even from a non-aqueous solution.
実施例7
供試材
供試材には板厚が0.2mmのSUS304 3/4Hを使用した。これを15mm×50mmに切断して試験片とした。
Example 7
Test material SUS304 3 / 4H with a thickness of 0.2 mm was used as the test material. This was cut into 15 mm × 50 mm to obtain test pieces.
実験方法
試験片をアセトン中に浸漬して超音波洗浄を施した後、1kmol・m-3LiOH水溶液中で1A/dm2で1分間のカソード電解を行い、蒸留水洗浄〜冷風乾燥を行なった後、200℃で10分間の大気加熱を行なった。
結果
図6に素材（SUS304 3/4H）と処理材の接触荷重-接触電気抵抗分布曲線を示す。このように、ばね材であるSUS304 3/4Hでも接触電気抵抗の急激な低下が認められた。
Experimental method After immersing the test piece in acetone and subjecting it to ultrasonic cleaning, cathode electrolysis was carried out at 1A / dm 2 for 1 minute in 1kmol · m -3 LiOH aqueous solution, followed by washing with distilled water and drying with cold air Thereafter, atmospheric heating was performed at 200 ° C. for 10 minutes.
Results Fig. 6 shows the contact load-contact electrical resistance distribution curve of the material (SUS304 3 / 4H) and the treated material. Thus, a sudden decrease in the contact electrical resistance was observed even with SUS304 3 / 4H as a spring material.
Claims (10)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007119693A JP5315571B2 (en) | 2007-04-27 | 2007-04-27 | Stainless steel conductive member and manufacturing method thereof |
| TW97114452A TWI427159B (en) | 2007-04-27 | 2008-04-21 | Conductive member made of stainless steel and manufacturing method thereof |
| TW101130212A TWI444506B (en) | 2007-04-27 | 2008-04-21 | Stainless steel conductive member and method for preparing the same |
| PCT/JP2008/057735 WO2008136306A1 (en) | 2007-04-27 | 2008-04-22 | Electroconductive member of stainless steel and process for producing the electroconductive member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007119693A JP5315571B2 (en) | 2007-04-27 | 2007-04-27 | Stainless steel conductive member and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008277145A JP2008277145A (en) | 2008-11-13 |
| JP5315571B2 true JP5315571B2 (en) | 2013-10-16 |
Family
ID=40054860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007119693A Active JP5315571B2 (en) | 2007-04-27 | 2007-04-27 | Stainless steel conductive member and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5315571B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6167411B2 (en) * | 2012-03-08 | 2017-07-26 | 株式会社ケミカル山本 | Surface modification treatment method of stainless steel with excellent resistance to chlorine pitting corrosion, overall corrosion resistance and rust prevention |
| JP2024004667A (en) * | 2022-06-29 | 2024-01-17 | 勝規 瀬川 | Electrolyte for modifying the surface of stainless steel |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3432454B2 (en) * | 1999-05-24 | 2003-08-04 | 日本金属株式会社 | Passivated stainless steel and method for producing the same |
| JP3668147B2 (en) * | 2001-03-15 | 2005-07-06 | 日本金属株式会社 | Stainless steel plate with excellent coating film adhesion, coated stainless steel plate, and production method thereof |
| JP4786576B2 (en) * | 2007-03-23 | 2011-10-05 | 日新製鋼株式会社 | Stainless steel material excellent in temper color resistance and its manufacturing method |
-
2007
- 2007-04-27 JP JP2007119693A patent/JP5315571B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008277145A (en) | 2008-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5077479B1 (en) | Contacts and electronic parts using the same | |
| JP5190726B2 (en) | Stainless steel conductive member and manufacturing method thereof | |
| TW201700796A (en) | Tin-plated product and method for producing same | |
| JP5309385B2 (en) | Stainless steel conductive member and manufacturing method thereof | |
| JP5315575B2 (en) | Al-containing ferritic stainless steel conductive member and method for producing the same | |
| JP2007291510A (en) | Silver-coated composite material for movable contact and method for producing the same | |
| JP5315571B2 (en) | Stainless steel conductive member and manufacturing method thereof | |
| JP5392016B2 (en) | Conductive stainless steel material and manufacturing method thereof | |
| JP4522970B2 (en) | Cu-Zn alloy heat resistant Sn plating strip with reduced whisker | |
| JP5464876B2 (en) | Sn-coated copper or copper alloy and method for producing the same | |
| JP2009099548A (en) | Silver-coated composite material for movable contact and method for producing the same | |
| JP2018193578A (en) | Tin-plated copper terminal material and terminal and wire terminal structure | |
| JP2011099128A (en) | Plated member and method for manufacturing the same | |
| EP2902533A1 (en) | Silver plating material and method for manufacturing same | |
| TWI444506B (en) | Stainless steel conductive member and method for preparing the same | |
| JP5315576B2 (en) | Si-containing ferritic stainless steel conductive member and method for producing the same | |
| JP4980266B2 (en) | High corrosion resistance plated steel material and method for producing the same | |
| JP2019112666A (en) | Conductive material | |
| KR100243368B1 (en) | Heat treatment method of lead frame | |
| JP5226032B2 (en) | Cu-Zn alloy heat resistant Sn plating strip with reduced whisker | |
| JP5598851B2 (en) | Silver-coated composite material for movable contact part, method for producing the same, and movable contact part | |
| JP5190725B2 (en) | Stainless steel conductive member and manufacturing method thereof | |
| JP2009099550A (en) | Silver-coated composite material for movable contact and method for producing the same | |
| JP2016113647A (en) | Production method of stainless material coated with metal plating | |
| JP3561504B2 (en) | Stainless steel conductive member and method of manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100427 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121009 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121207 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130107 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130115 |
|
| 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: 20130617 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130621 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5315571 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 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 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |