WO2023033038A1 - めっき皮膜付端子材及び端子材用銅板 - Google Patents
めっき皮膜付端子材及び端子材用銅板 Download PDFInfo
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- WO2023033038A1 WO2023033038A1 PCT/JP2022/032751 JP2022032751W WO2023033038A1 WO 2023033038 A1 WO2023033038 A1 WO 2023033038A1 JP 2022032751 W JP2022032751 W JP 2022032751W WO 2023033038 A1 WO2023033038 A1 WO 2023033038A1
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- Prior art keywords
- copper
- kam value
- plating film
- base material
- less
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- 239000000463 material Substances 0.000 title claims abstract description 119
- 238000007747 plating Methods 0.000 title claims abstract description 106
- 239000010949 copper Substances 0.000 title claims abstract description 61
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 59
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 56
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910001128 Sn alloy Inorganic materials 0.000 claims abstract description 8
- 238000001887 electron backscatter diffraction Methods 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 42
- 239000000758 substrate Substances 0.000 claims description 16
- 239000010410 layer Substances 0.000 description 56
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 45
- 229910052718 tin Inorganic materials 0.000 description 28
- 238000005259 measurement Methods 0.000 description 23
- 229910052759 nickel Inorganic materials 0.000 description 22
- 238000005452 bending Methods 0.000 description 17
- 238000005498 polishing Methods 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 238000005422 blasting Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000956 alloy Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000006061 abrasive grain Substances 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910017755 Cu-Sn Inorganic materials 0.000 description 2
- 229910017927 Cu—Sn Inorganic materials 0.000 description 2
- 101100373498 Enterobacteria phage T4 y06L gene Proteins 0.000 description 2
- 101100373501 Enterobacteria phage T4 y06O gene Proteins 0.000 description 2
- 108010057081 Merozoite Surface Protein 1 Proteins 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 101100494770 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CAT8 gene Proteins 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000007405 data analysis Methods 0.000 description 2
- 238000013480 data collection Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000000992 sputter etching Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 1
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 1
- 229910017824 Cu—Fe—P Inorganic materials 0.000 description 1
- 229910017876 Cu—Ni—Si Inorganic materials 0.000 description 1
- 229910017985 Cu—Zr Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004837 P—Sn Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- -1 straining treatment Substances 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
- C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/02—Contact members
- H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
Definitions
- the present invention relates to a terminal material with a plating film and a copper plate for the terminal material, which has excellent adhesion of the plating film.
- a terminal material with a plating film which is a plate material made of copper or copper alloy and tin-plated, is used as a material for electrical connection terminals and connector contacts.
- a copper alloy containing 0.3% to 15% by mass of Ni is used as a base material, and a Sn-plated layer is formed on the surface by reflow or hot-dip Sn plating, and the Sn-plated layer is formed from the surface layer side. It consists of an Sn layer with a thickness of 0.5 ⁇ m or less and a Cu—Sn alloy layer of columnar crystals with an average cross-sectional diameter of 0.05 to 1.0 ⁇ m and an average aspect ratio of 1 or more, and the Sn plating layer (Sn layer and Cu—Sn A Sn-plated copper alloy material in which the alloy layer) has a thickness of 0.2 to 2.0 ⁇ m is described.
- Patent Document 3 in order to improve the tin plating adhesion of the Ni—P—Sn-based copper alloy plate, the surface is cleaned by mechanical polishing after the heat treatment is completed, and the thickness of the work-affected layer on the surface layer is reduced to 0.4 ⁇ m or less.
- a copper alloy plate with the following characteristics is disclosed.
- tin-plated plated materials are also used as contacts for automobile connectors, and depending on the environment in which the automobile is used, intense vibration and heat may be applied to the connector, resulting in insufficient adhesion of the plating layer. There was something that happened.
- An object of the present invention is to provide a terminal material with a plating film and a copper sheet for the terminal material that can suppress the occurrence of cracks during bending.
- the terminal material with a plated film of the present invention has a base material made of copper or a copper alloy and a plated film formed on the base material,
- the plating film has a tin layer made of tin or a tin alloy,
- the surface portion KAM value measured by analyzing the cross section of the surface portion in the range of 1 ⁇ m in depth in the thickness direction of the base material from the interface between the base material and the plating film by the EBSD method is 0.15 ° or more 0 is less than 0.90°, and the center KAM value at the thickness center of the base material is 0.1 times or more and 0.6 times or less the surface KAM value.
- the KAM (Kernel Average Misorientation) value is the average value of the orientation difference between adjacent measurement points measured by the EBSD (Electron Back Scattered Diffraction) method, and represents the local change in crystal orientation. A larger value indicates a larger strain.
- the KAM value of the surface portion is set to be larger than the KAM value of the center portion. In this state, the strength near the interface is improved, and the adhesion of the plating film is increased. If the KAM value of the surface portion is less than 0.15°, the strain is small and the strength near the interface is poor, so that improvement in adhesion cannot be expected. If the angle is 0.90° or more, the mutual diffusion rate between the copper in the substrate and the tin in the film becomes too fast due to the effect of excessive strain, which induces Kirkendall voids and reduces adhesion.
- the central KAM value is the original KAM value of the base material, which is relatively low compared to the surface KAM value.
- KAM values do not change much even in a high temperature environment, and not only does it improve adhesion at the initial stage of manufacturing, but also prevents peeling of the plating film and improves heat resistance when a heat load is applied during use. can also suppress the occurrence of cracks.
- the average grain size of the surface portion is 0.5 ⁇ m or more and 3.0 ⁇ m or less.
- the average grain size of the surface portion When the average grain size of the surface portion is large, the diffusion of tin in the plating film to the copper of the base material is suppressed, so that the interdiffusion of copper and tin is balanced and the occurrence of Kirkendall voids can be suppressed. As a result, it is effective in preventing peeling of the plating film. If the average crystal grain size is less than 0.5 ⁇ m, the effect of suppressing the diffusion of tin is poor.
- the average crystal grain size of the central portion is preferably greater than the average crystal grain size of the surface portion and is 1.5 ⁇ m or more and 10 ⁇ m or less.
- the substrate is preferably a Mg-containing copper alloy containing 0.2% by mass or more and 2.0% by mass or less of Mg.
- Mg-containing copper alloys are generally suitable for terminal materials due to their high strength, but they lack adhesion to plating films as they are. Adhesion of the plating film can be enhanced by using the terminal material of the present invention.
- the copper plate for terminal material of the present invention is a plate material made of copper or copper alloy, and the surface portion KAM measured by analyzing the cross section of the surface portion in the range of 1 ⁇ m in depth from the surface in the thickness direction of the plate material by the EBSD method.
- the value is 0.15° or more and less than 0.90°
- the central portion KAM value at the plate thickness central portion of the plate material is 0.1 times or more and 0.6 times or less the surface portion KAM value.
- This copper plate for terminal material can be a Mg-containing copper alloy plate containing 0.2% by mass or more and 2.0% by mass or less of Mg.
- Mg-containing copper alloys are generally suitable for terminal materials due to their high strength, but they lack adhesion to plating films as they are. By applying this invention, the adhesion of the plating film can be enhanced.
- the surface portion KAM value and the ratio of the KAM value between the surface portion and the center portion are set within a predetermined range, so that the adhesion of the plating film is improved, and not only the adhesion at the initial stage of production but also the use Prevents peeling of the plating film even when a heat load is applied, and improves heat resistance.
- FIG. 1 is a cross-sectional view schematically showing a first embodiment of a plated film terminal material of the present invention
- FIG. 2 is a cross-sectional view schematically showing a second embodiment of the plated film terminal material of the present invention
- the terminal material 1 with a plated film of the first embodiment has a plated film 3 formed on the surface of the substrate 2, and the KAM value of the surface portion S1 of the substrate 2 (surface portion KAM value), and the ratio between the surface KAM value and the center KAM value at the center of the plate thickness are set within a specific range.
- the substrate 2 is a plate material (copper plate for terminal material) made of copper or a copper alloy, and preferably contains 0.2% by mass or more and 2.0% by mass or less of Mg.
- Mg-containing copper alloy containing 0.3% by mass or more and 1.2% by mass or less of Mg, 0.001% by mass or more and 0.2% by mass or less of P, and the balance being Cu and unavoidable impurities is a mechanical It can be preferably used because of its high mechanical strength.
- a Mg-containing copper alloy containing more than 1.2% by mass and not more than 2.0% by mass of Mg, the balance being Cu and unavoidable impurities can also be applied.
- Mg-containing copper alloys include Mg-containing copper alloys "MSP" series (MSP1, MSP5, MSP8) manufactured by Mitsubishi Materials Corporation.
- the base material 2 has a surface KAM value of 0.15° or more and less than 0.90°, which is measured by analyzing a cross section of the surface portion within a depth of 1 ⁇ m from the surface by the EBSD method. is 0.1 times or more and 0.6 times or less of the surface portion KAM value at the center of the sheet thickness (referred to as the center KAM value).
- the base material 2 has an average crystal grain size of 0.5 ⁇ m or more and 3.0 ⁇ m or less in the surface portion (a range of 1 ⁇ m in depth from the surface), and the average crystal grain size of the central portion is the average of the surface portion It exceeds the crystal grain size and is preferably 1.5 ⁇ m or more and 10 ⁇ m or less. These crystal grain sizes are measured using the EBSD method similar to the measurement of the KAM value.
- Measurement of the KAM value and grain size by the EBSD method is carried out as follows. After mechanically polishing a longitudinal section (surface viewed in the TD direction) including the plating film 3 along the rolling direction (RD direction) of the base material 2 using water-resistant abrasive paper and diamond abrasive grains, Ar ion cross-section processing. The measurement surface was processed using an apparatus (Ion milling apparatus IM4000 manufactured by Hitachi High-Tech Co., Ltd.). For crystal orientation measurement using Kernel Average Misorientation (KAM) and electron backscatter diffraction for calculating crystal grain size, an EBSD measuring device (Hitachi High-Tech Co., Ltd.
- the acceleration voltage of the electron beam of the EBSD measurement device was 15 kV
- the measurement field was 3 ⁇ m ⁇ 5 ⁇ m (plating thickness direction ⁇ plating surface horizontal direction)
- the crystal orientation measurement step size was 0.01 ⁇ m.
- the data obtained by the EBSD measurement device is processed using analysis software, and the portion where the difference in crystal orientation between adjacent measurement points is 5° or more is regarded as a grain boundary, and the KAM value and grain size are measured. do.
- a range of 1 ⁇ m in depth from the interface between the base material 2 and the plating film 3 in the thickness direction of the base material and the average value of the crystal grain size and the KAM value in the thickness center of the base material were calculated.
- the plating film 3 formed on the substrate 2 has a copper-tin alloy layer 4 made of an alloy of copper and tin, and a tin layer 5 made of tin or a tin alloy thereon.
- a copper-tin alloy layer 4 made of an alloy of copper and tin
- a tin layer 5 made of tin or a tin alloy thereon.
- each layer 4 and 5 of the plating film 3 is not particularly limited, for example, the copper-tin alloy layer 4 has a thickness of 0.1 ⁇ m to 1.5 ⁇ m, and the tin layer 5 has a thickness of 0.1 ⁇ m. ⁇ 3.0 ⁇ m.
- the KAM value of the surface portion is a value in the range from the interface between the base material 2 and the copper-tin alloy layer 4 to a depth of 1 ⁇ m in the thickness direction of the base material 2, and the KAM value measured at a portion with a thickness of 1 ⁇ m. is the average value of
- the range indicated by symbol S1 in FIG. 1 is the surface portion, and the position indicated by B1 is the interface between the surface portion S1 and the plating film 3 .
- a nickel layer made of nickel or a nickel alloy may be formed between the base material 2 and the copper-tin alloy layer 4 as necessary.
- FIG. 1 shows an embodiment without a nickel layer and FIG. 2 shows a second embodiment with a nickel layer.
- the plating film 6 formed on the surface of the base material 2 includes a nickel layer 7 made of nickel or a nickel alloy, A copper-tin alloy layer 4 made of copper and a tin layer 5 made of tin or a tin alloy are formed in this order.
- the nickel layer 7 can prevent diffusion of copper from the base material 2 and improve heat resistance.
- the KAM value of the range S2 of 1 ⁇ m in depth from the interface B2 between the base material 2 and the nickel layer 7 in the thickness direction of the base material 2 is the surface part KAM value.
- the grain size of the range S2 is the grain size of the surface portion.
- a copper ingot made of copper or a copper alloy is subjected to hot rolling, cold rolling, annealing, finish cold rolling, etc. to produce a copper mother plate, and the copper mother plate is surface-treated to form a base material (this Copper plate for terminal material of the invention).
- This surface processing is processing for selectively imparting strain to the surface portion S1 by mechanically processing the surface of the copper mother plate. Specifically, wet blasting is preferred.
- the wet blasting method is a method of processing the surface by spraying a mixture (slurry) of water and an abrasive onto the surface of the copper mother plate. Since the abrasive is mixed with water, the abrasive along with the particles scraped off from the surface of the copper mother board is washed away with the water and does not remain on the surface of the copper mother board. It is preferable to use spherical abrasive grains as the abrasive.
- the dry blasting method is not preferable because the abrasive may remain on the surface of the copper mother plate.
- Mechanical polishing such as buffing can also be applied.
- the surface of the copper mother plate tends to become a fine structure, and the crystal grain size and KAM value do not reach desired values. If the surface is distorted by buffing, post-processing such as removing fine structures by etching or the like is required.
- the wet blast method does not require any post-processing.
- a chemical polishing treatment is performed as necessary.
- a solution (chemical polishing liquid) having a sulfuric acid concentration of 50 g/L, a hydrogen peroxide concentration of 5 g/L, and a chloride ion concentration of 30 mg/L is used, and the copper mother plate is polished at a bath temperature of 30° C. for 1 minute. Immersion treatment.
- the excess strain portion is removed when excessive strain is applied. Whether or not the strain is excessively applied can be judged from the measurement result of the KAM value by the following EBSD method.
- the excessively strained portion is located on the surface of the copper mother plate, it can be removed by chemically polishing the copper mother plate to an appropriate thickness.
- the chemical polishing treatment can be carried out by a method such as spraying the chemical polishing liquid onto the copper mother board in addition to the treatment of immersing the copper mother board in the chemical polishing liquid.
- the base material 2 (copper plate for terminal material) in which the copper mother plate has been subjected to surface processing has a surface portion S1 within a depth of 1 ⁇ m from the surface of the surface portion S1 measured by the EBSD method. is 0.15° or more and less than 0.90°, and the central portion KAM value at the plate thickness central portion of the base material 2 is 0.1 times or more and 0.6 times or less the surface portion KAM value.
- the center KAM value is substantially the same as the KAM value at the center of the thickness of the copper mother plate.
- the central portion of the thickness is a region from the surface in the thickness direction from the position of 40% to the position of 60% of the total thickness.
- the average crystal grain size of the surface portion S1 of the substrate 2 is 0.5 ⁇ m or more and 3.0 ⁇ m or less, and the average crystal grain size of the central portion exceeds the average crystal grain size of the surface portion S1 and is 1.5 ⁇ m or more. Most of them are 10 ⁇ m or less.
- plating is performed to form the plating film 3 on the surface of the base material 2 .
- the surface of the base material 2 is subjected to degreasing, pickling, or the like to remove dirt and natural oxide film, and then copper plating treatment and tin plating treatment are sequentially applied thereon, followed by reflow treatment. do.
- the plating layer is formed on both surfaces of the substrate 2 .
- a general copper plating bath may be used for the copper plating treatment, and for example, a copper sulfate bath containing copper sulfate (CuSO 4 ) and sulfuric acid (H 2 SO 4 ) as main components may be used.
- the temperature of the plating bath is 20-50° C., and the current density is 1-30 A/dm 2 .
- a general tin plating bath may be used.
- a sulfuric acid bath containing sulfuric acid (H 2 SO 4 ) and stannous sulfate (SnSO 4 ) as main components may be used. can be done.
- the temperature of the plating bath is 15-35° C., and the current density is 1-30 A/dm 2 .
- the material after plating is heated, for example, at 240°C to 300°C for 3 to 15 seconds in a heating furnace in a reducing atmosphere, and then cooled.
- the copper of the copper plating layer preferentially diffuses into the grain boundaries of the tin before the tin plating layer melts to form an intermetallic compound and form the copper-tin alloy layer 4. .
- a part of the tin plating layer remains, a tin layer 5 is formed on the copper-tin alloy layer 4 , and a plating film 3 composed of the copper-tin alloy layer 4 and the tin layer 5 is formed on the surface of the substrate 2 .
- a copper layer may be formed between the copper-tin alloy layer and the base material due to part of the copper-plated layer remaining. In this case, the crystal structure of the copper layer has grown so that the surface state of the base material is transferred.
- the KAM value may be measured as the surface portion KAM value at a surface portion within a depth of 1 ⁇ m in the thickness direction from the interface with the layer.
- the nickel layer 7 is formed on the surface of the base material 2 as necessary, but when the nickel layer 7 is provided, the nickel plating process is performed before the copper plating process.
- a general nickel plating bath may be used for the nickel plating treatment for forming the nickel plating layer.
- a sulfuric acid bath containing sulfuric acid (H 2 SO 4 ) and nickel sulfate (NiSO 4 ) as main components may be used. can be done.
- the temperature of the plating bath is 20° C. or higher and 60° C. or lower, and the current density is 5 to 60 A/dm 2 .
- the film thickness of the nickel plating layer is, for example, 0.05 ⁇ m or more and 1.0 ⁇ m or less.
- the KAM value of the surface portion is set larger than the KAM value of the central portion. It is in a state in which strain is selectively applied, and the strength near the interface is improved, and the strength of the joint is improved. As a result, the adhesion of the plating film 3 is increased. If the KAM value of the surface portion is less than 0.15°, the strain is small and the strength near the interface is poor, so that improvement in adhesion cannot be expected. If it is 0.90° or more, the interdiffusion rate between the copper in the base material 2 and the tin in the plating film 3 becomes too fast, which induces Kirkendall voids and reduces the adhesion.
- the central KAM value is the original KAM value of the base material 2, which is relatively lower than the KAM value of the surface area. Granted. If the KAM value of the central part is less than 0.1 times the KAM value of the surface part, the strain imparted to the surface becomes excessive with respect to the inside of the base material, and when bending is applied, stress concentrates near the surface and plating fails. Easy to peel off. If it exceeds 0.6 times, the strain is accumulated inside the base material, and cracks are likely to occur in the base material when bending is performed.
- the KAM value does not change much even in a high-temperature environment, and not only does it improve adhesion at the initial stage of manufacturing, but it also prevents the plating film from peeling off when a heat load is applied during use, improving heat resistance and bending. It is also possible to suppress the occurrence of cracks when the temperature is reduced.
- a preferable surface portion KAM value is 0.30° or more and 0.60° or less, and a ratio of the central portion KAM value to the surface portion KAM value is preferably 0.2 times or more and 0.4 times or less. It should be noted that it is possible to increase the KAM value not only of the surface portion S1 of the base material 2 but also of the entire base material 2 by, for example, increasing the rolling reduction during rolling. This is not preferable because it also changes the material properties.
- the average crystal grain size of the surface portion S1 is large, the diffusion of tin in the plating film 3 to the copper of the base material 2 is suppressed, so that the interdiffusion of copper and tin is balanced and Kirkendall voids are formed. As a result of being able to suppress the occurrence of , it is effective in preventing the peeling of the plating film 3 .
- the average grain size of the surface portion S1 is preferably 0.5 ⁇ m or more and 3.0 ⁇ m or less, more preferably 0.6 ⁇ m or more and 1.5 ⁇ m or less.
- the Mg-containing copper alloy of the base material 2 the "MSP" series (MSP1, MSP5, MSP8) manufactured by Mitsubishi Materials Corporation was exemplified.
- Cu-Ni-Si-based alloy (MAX2251), Cu-Fe-P-based alloy (TAMAC194), Cu-Zr-based alloy (C151), Cu-Cr-Zr-based alloy (MZC1), Cu- A Zn--Ni--Sn alloy (MNEX10) may also be used.
- the control of the KAM value and average grain size of the surface portion is achieved by sequentially performing appropriate strain imparting treatment by physical treatment and chemical polishing treatment for removing excessively strained portions.
- a plate material of a copper alloy having the composition shown in Table 1 was prepared as a base material, the surface was subjected to a strain imparting treatment by wet blasting, and alkaline electrolytic degreasing was performed to remove abrasive grains used in the blasting treatment. After that, a chemical polishing process was performed to selectively remove the excessively strained portion.
- samples without wet blasting treatment and samples with only wet blasting treatment without chemical polishing treatment were also produced.
- the plate material was pickled and plated with copper. Depending on the sample, copper plating was applied after nickel plating. After the copper plating, each sample shown in Table 1 was produced by tin plating and reflow treatment.
- the thickness of the tin plating layer was 1 ⁇ m
- the thickness of the copper plating layer was 0.5 ⁇ m
- the thickness of the nickel plating layer was 0.5 ⁇ m.
- the wet blasting was carried out by spraying a slurry containing 5 vol % of spherical zirconia with a particle size of 40 ⁇ m under the conditions of an air pressure of 0.4 MPa and a projection angle of 45°.
- KAM value and crystal grain size of the central portion of the substrate depend on the KAM value and crystal grain size of the prepared substrate itself, substrates of materials with different KAM values and crystal grain sizes were prepared. Since the KAM value and crystal grain size of the surface portion are determined by the prepared base material, straining treatment, and chemical polishing treatment, wet blasting treatment and chemical polishing treatment are performed so as to obtain the desired KAM value and crystal grain size. adjusted the time.
- the KAM value and crystal grain size of the surface portion and the center portion were measured by the method described above, and an adhesion test was performed.
- a longitudinal section (surface viewed in the TD direction) including the plating layer along the rolling direction (RD direction) of each sample was mechanically polished using water-resistant abrasive paper and diamond abrasive grains, and then an Ar ion cross-section processing device ( The measurement surface was processed using an ion milling device IM4000 (manufactured by Hitachi High-Tech Co., Ltd.).
- an EBSD measurement device (scanning electron microscope SU5000 manufactured by Hitachi High-Tech Co., Ltd., OIM manufactured by EDAX / TSL) Data Collection) and analysis software (OIM Data Analysis ver.7.3 manufactured by EDAX/TSL) were used.
- the acceleration voltage of the electron beam of the EBSD measurement device was 15 kV
- the measurement field was 3 ⁇ m ⁇ 5 ⁇ m (plating thickness direction ⁇ plating surface horizontal direction)
- the crystal orientation measurement step size was 0.01 ⁇ m.
- the data obtained by the EBSD measurement device is processed using analysis software, and the portion where the difference in crystal orientation between adjacent measurement points is 5° or more is regarded as a grain boundary, and the KAM value and grain size are measured. bottom.
- the crystal grain size is determined by the major axis of the crystal grain (the length of the longest straight line that can be drawn in the grain under the condition that it does not touch the grain boundary in the middle) and the minor axis (the direction that intersects the major axis at right angles, under the condition that it does not touch the grain boundary in the middle).
- the length of the straight line that can be drawn longest in the grain was calculated by the average value.
- the KAM value was calculated by calculating the average value of the orientation difference between a specific measurement point in a crystal grain and the adjacent measurement points in the same crystal grain, and calculating the average value for all crystal grains arranged in the measurement field.
- the KAM value and the average crystal grain size were calculated for a range of 1 ⁇ m in depth from the interface with the plated film in the thickness direction of the substrate and for the central portion of the plate thickness of the substrate.
- "A” indicates that no cracks, etc. were observed and the surface condition did not change significantly before and after bending, and "B” indicates that changes in surface condition such as a decrease in gloss were observed, but no cracks could be confirmed.
- adhesion after heating the sample is evaluated, if the evaluation of adhesion after heating is good, it can be said that the adhesion before heating, that is, immediately after production is also excellent. has not been implemented.
- the surface KAM value is 0.15° or more and less than 0.90°, and the central KAM value is 0.1 times or more and 0.6 times or less than the surface KAM value. All of them were evaluated as “C” or higher in the adhesion test, and it was found that the adhesion of the plating film after heating was excellent.
- the bending workability was "C” or higher, and the bending workability was also excellent.
- Examples 5 to 9, in which the surface portion average particle diameter was 0.5 ⁇ m or more and 3.0 ⁇ m or less, were evaluated as “B” or higher in the adhesion test and were excellent.
- the average crystal grain size at the central portion of Examples 5 to 9 was within the range of 1.5 ⁇ m or more and 10 ⁇ m or less.
- Example 5 having a nickel layer was evaluated as "A" in the adhesion test and was particularly excellent. As described above, the adhesion before heating the sample, that is, immediately after production, is superior to the adhesion test results in Table 2.
- the surface portion KAM value is as small as 0.10°, and the magnification of the surface portion KAM value to the central portion KAM value is as large as 0.7 times.
- the value is as large as 1.00° and the KAM value magnification is as small as 0.05.
- the surface portion KAM value is as large as 1.50° and the KAM value magnification is as large as 10.0 Peeling of the plating film was also observed in the adhesion test.
- the surface KAM value is in the range of 0.15 ° or more and less than 0.90 °, but in Comparative Examples 4 and 5, the central KAM value with respect to the surface KAM value In both cases, the magnification was large, and cracks occurred during bending and were inferior. Moreover, in Comparative Examples 2 and 6, since the magnification was as small as 0.05 times and 0.07 times, peeling of the plating occurred due to the influence of bending. . Conversely, in Comparative Examples 7 and 8, the ratio of the central KAM value to the surface KAM value is 0.1 times or more and 0.6 times or less, but in Comparative Example 7, the surface KAM value is 0.12. In Comparative Example 8, the KAM value of the surface portion was as large as 1.00, so peeling of the plating film was observed in the adhesion test.
- Terminal material with plated film 2 Base material 3 6 Plated film 4 Copper-tin alloy layer 5 Tin layer 7 Nickel layer S1, S2 Surface parts B1, B2 Interface
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Abstract
Description
ロー処理されたSnまたはSn合金めっき表層とからなり,該中間層が陰極電流密度2~20A/dm2の条件でめっきした曲げ性と挿抜性に優れたコネクタ用めっき材料が記載されている。
前記めっき皮膜は錫又は錫合金からなる錫層を有し、
前記基材と前記めっき皮膜との界面から前記基材の厚さ方向に深さ1μmの範囲の表面部の断面をEBSD法により解析して測定される表面部KAM値が0.15°以上0.90°未満であり、前記基材の板厚中心部における中心部KAM値が前記表面部KAM値の0.1倍以上0.6倍以下である。
その平均結晶粒径が0.5μm未満に微細になると、錫の拡散を抑制する効果に乏しく、3.0μmを超えると逆に銅の拡散の方が多くなってボイドが生じるおそれがある。
Mg含有銅合金は、一般に、強度が高いため端子材に好適であるが、そのままではめっき皮膜の密着性に乏しい。この発明の端子材とすることにより、めっき皮膜の密着性を高めることができる。
この端子材用銅板にめっきを施すと、そのめっき皮膜との密着性が良く、剥離を抑制できる。
Mg含有銅合金は、一般に、強度が高いため端子材に好適であるが、そのままではめっき皮膜の密着性に乏しい。この発明を適用することにより、めっき皮膜の密着性を高めることができる。
基材2は、銅又は銅合金からなる板材(端子材用銅板)であり、0.2質量%以上2.0質量%以下のMgを含有しているとよい。例えば、0.3質量%以上1.2質量%以下のMgと、0.001質量%以上0.2質量%以下のPとを含み、残部がCuおよび不可避不純物からなるMg含有銅合金は機械的強度が高いので、好適に用いることができる。1.2質量%を超え、2.0質量%以下のMgを含み、残部がCuおよび不可避不純物からなるMg含有銅合金も適用できる。このようなMg含有銅合金としては、三菱マテリアル株式会社製のMgを含有する銅合金「MSP」シリーズ(MSP1、MSP5、MSP8)が挙げられる。
これら結晶粒径は、KAM値の測定と同様のEBSD法を用いて測定される。
基材2の圧延方向(RD方向)に沿う、めっき皮膜3を含む縦断面(TD方向に見た面)を耐水研磨紙、ダイヤモンド砥粒を用いて機械研磨を行った後、Arイオン断面加工装置(株式会社日立ハイテク製 イオンミリング装置IM4000)を用いて測定面の加工を行った。Kernel Average Misorientation(KAM)及び結晶粒径を算出するための電子後方散乱回折を用いた結晶方位測定には、EBSD測定装置(株式会社日立ハイテク製 走査型電子顕微鏡SU5000、EDAX/TSL社製 OIM Data Collection)と、解析ソフト(EDAX/TSL社製 OIM Data Analysis ver.7.3)を用いた。EBSD測定装置の電子線の加速電圧は15kV,測定視野は3μm×5μm(めっき厚さ方向×めっき面水平方向)、結晶方位測定の測定点間隔(Step Size)は0.01μmとした。EBSD測定装置で得られたデータを,解析ソフトを用いて処理し,隣接する測定点間の結晶方位の差が5°以上の部位を結晶粒界とみなして、KAM値及び結晶粒径を測定する。
基材2上に形成されるめっき皮膜3は、この実施形態では、銅と錫との合金からなる銅錫合金層4と、その上の錫又は錫合金からなる錫層5とを有している。なお、図1等には基材2の片面のみ拡大して示しているが、めっき皮膜3は基材2の片面のみに形成される場合と、基材2の両面に形成される場合とがある。
この図2に示す第2実施形態のめっき皮膜付端子材11においては、基材2の表面に形成されるめっき皮膜6は、ニッケル又はニッケル合金からなるニッケル層7、銅と錫との合金からなる銅錫合金層4、錫又は錫合金からなる錫層5がこの順に形成されている。ニッケル層7が基材2からの銅の拡散を防止して、耐熱性を向上させることができる。
これら表面部KAM値、表面部の結晶粒径、中心部KAM値、及び中心部の結晶粒径は、ニッケル層を有しないめっき皮膜付端子材1の場合と同じである。
以上のように構成されるめっき皮膜付端子材1を製造する方法について説明する。以下では、図1に示すめっき皮膜付端子材1の製造方法を中心に説明し、必要に応じて図2に示すめっき皮膜付端子材11の製造方法を説明する。
銅又は銅合金からなる銅鋳塊に、熱間圧延、冷間圧延、焼鈍、仕上げ冷間圧延等を施して銅母板を製造し、この銅母板に表面加工を施して基材(本発明の端子材用銅板)とする。
また、バフ研磨等の機械研磨を施すこともできる。ただし、バフ研磨等の機械研磨の場合は、銅母板の表面が微細組織になり易く結晶粒径およびKAM値が所望の値にならない。バフ研磨で表面に歪を与えた場合は、エッチング等によって微細組織を除去するなどの後加工が必要になる。ウエットブラスト法は後加工も不要である。
化学研磨処理は、例えば、硫酸濃度50g/L,過酸化水素濃度5g/L,塩化物イオン濃度30mg/Lの溶液(化学研磨液)を用いて、浴温30℃で銅母板を1分間浸漬処理する。この化学研磨処理を実施することにより、過剰に歪が付与された場合に、歪過剰部が除去される。過剰に歪が付与されたか否かは、次のEBSD法によるKAM値の測定結果により判断できる。
歪過剰部は、銅母板の表面に位置するため、銅母板を適切な厚さで化学研磨することで除去できる。化学研磨処理は化学研磨液に銅母板を浸漬する処理以外にも、銅母板に化学研磨液をスプレー噴射する、などの方法によっても行うことができる。
次に、この基材2の表面にめっき皮膜3を形成するためにめっき処理を行う。
めっき処理としては、基材2の表面に脱脂、酸洗等の処理をすることによって、汚れおよび自然酸化膜を除去した後、その上に、銅めっき処理、錫めっき処理を順に施し、リフロー処理する。なお、めっき層は基材2の両面に形成される。
れる。ニッケルめっき層の膜厚は例えば0.05μm以上1.0μm以下とされる。
この場合、KAM値は高温環境下でも変化が少なく、製造初期の密着性だけでなく、使用時に熱負荷がかかった際にもめっき皮膜の剥離を防止して耐熱性が向上するとともに、曲げ加工時のクラックの発生も抑制することができる。
なお、基材2の表面部S1だけでなく、全体のKAM値が大きい値とすることは、例えば圧延時の圧下率を大きくするなどにより可能であるが、その場合は、基材2本来の材料特性も変化してしまうので好ましくない。
各試料の圧延方向(RD方向)に沿う、めっき層を含む縦断面(TD方向に見た面)を耐水研磨紙、ダイヤモンド砥粒を用いて機械研磨を行った後、Arイオン断面加工装置(株式会社日立ハイテク社製 イオンミリング装置IM4000)を用いて測定面の加工を行った。Kernel Average Misorientation(KAM)及び結晶粒径を算出するための電子後方散乱回折を用いた結晶方位測定には、EBSD測定装置(株式会社日立ハイテク社製 走査型電子顕微鏡SU5000、EDAX/TSL社製 OIM Data Collection)と、解析ソフト(EDAX/TSL社製 OIM Data Analysis ver.7.3)を用いた。EBSD測定装置の電子線の加速電圧は15kV,測定視野は3μm×5μm(めっき厚さ方向×めっき面水平方向)、結晶方位測定の測定点間隔(Step Size)は0.01μmとした。EBSD測定装置で得られたデータを,解析ソフトを用いて処理し,隣接する測定点間の結晶方位の差が5°以上の部位を結晶粒界とみなして、KAM値及び結晶粒径を測定した。
サンプルを150℃の温度にて240時間大気雰囲気中で加熱した後、JIS H 8504のテープ試験方法にてめっき皮膜の密着性を評価した。また、試験を厳しく行うため、テープを貼る前に鋭利な刃物でめっき皮膜面に一辺が2mmの正方形が出来るように切り込みを入れ、テープを貼り付けた。テープを剥がし、めっき皮膜がテープにくっついて素材から剥がれてしまった(全体の50%以上剥がれた)ものを「D」、素材からめっき皮膜が一定量(全体の50%未満、5%以上)剥がれたものを「C」。素材からめっき皮膜が剥がれたが、微小な剥がれ(全体の5%未満)だったものを「B」、テープにめっき皮膜が付かず剥がれなかったものを「A」とした。評価「C」以上であれば、実用上の支障はない。
[曲げ加工性試験]
曲げ加工性は、試料をBadWay:圧延垂直方向に幅10mm×長さ60mmに切出し、JIS Z 2248に規定される金属材料曲げ試験方法に準拠し、曲げ半径Rと押し金具の厚さtとの比R/t=1として180°曲げ試験を行い、曲げ部の表面及び断面にクラック等が認められるか否かを光学顕微鏡にて倍率50倍で観察した。クラック等が認められず、表面状態も曲げの前後で大きな変化がなかったものを「A」、表面は光沢低下などの状態変化が認められたもののクラックの発生は確認できなかったものを「B」、クラックは認められたものの、めっき剥離は認められなかったものを「C」、めっき自体の剥離が認められたものを「D」とした。
なお、前述したように、サンプルを加熱する前、つまり製造直後の密着性は、表2の密着性試験結果よりも優れた結果となる。
また、比較例4~比較例5では、表面部KAM値は0.15°以上0.90°未満の範囲内であるものの、比較例4及び比較例5では表面部KAM値に対する中心部KAM値の倍率がいずれも大きく、曲げ加工時にクラックが発生し劣っていた。また、比較例2と6ではその倍率が0.05倍、0.07倍と小さいため、曲げ加工時の影響によりめっきの剥離が発生した。。逆に、比較例7及び比較例8は、表面部KAM値に対する中心部KAM値の倍率は0.1倍以上0.6倍以下であるが、比較例7では表面部KAM値が0.12と小さく、比較例8では表面部KAM値が1.00と大きいため、それぞれ密着性試験でめっき皮膜の剥がれが認められた。
2 基材
3,6 めっき皮膜
4 銅錫合金層
5 錫層
7 ニッケル層
S1,S2 表面部
B1,B2 界面
Claims (6)
- 銅又は銅合金からなる基材と、該基材の上に形成されためっき皮膜とを有し、
前記めっき皮膜は錫又は錫合金からなる錫層を有し、
前記基材と前記めっき皮膜との界面から前記基材厚さ方向に深さ1μmの範囲の表面部の断面をEBSD法により解析して測定される表面部KAM値が0.15°以上0.90°未満であり、前記基材の板厚中心部における中心部KAM値が前記表面部KAM値の0.1倍以上0.6倍以下であることを特徴とするめっき皮膜付端子材。 - 前記表面部の平均結晶粒径が0.5μm以上3.0μm以下であることを特徴とする請求項1に記載のめっき皮膜付端子材。
- 前記中心部の平均結晶粒径は、前記表面部の平均結晶粒径を超え、1.5μm以上10μm以下であることを特徴とする請求項2に記載のめっき皮膜付端子材。
- 前記基材は、0.2量%以上2.0質量%以下のMgを含有するMg含有銅合金であることを特徴とする請求項1から3のいずれか一項に記載のめっき皮膜付端子材。
- 銅又は銅合金からなる板材であり、表面から板材の厚さ方向に深さ1μmの範囲の表面部の断面をEBSD法により解析して測定される表面部KAM値が0.15°以上0.90°未満であり、前記板材の板厚中心部における中心部KAM値が前記表面部KAM値の0.1倍以上0.6倍以下であることを特徴とする端子材用銅板。
- 0.2質量%以上2.0質量%以下のMgを含有するMg含有銅合金であることを特徴とする請求項5に記載の端子材用銅板。
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JP (1) | JP7315120B1 (ja) |
CN (1) | CN117940613A (ja) |
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Citations (5)
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WO2011086978A1 (ja) * | 2010-01-12 | 2011-07-21 | 三菱マテリアル株式会社 | 電気銅めっき用含リン銅アノード、その製造方法および電気銅めっき方法 |
WO2011122493A1 (ja) * | 2010-03-30 | 2011-10-06 | 三菱マテリアル株式会社 | 電気銅めっき用高純度銅アノード、その製造方法および電気銅めっき方法 |
JP2012122114A (ja) * | 2010-12-10 | 2012-06-28 | Mitsubishi Shindoh Co Ltd | 深絞り加工性及び耐疲労特性に優れたCu−Ni−Si系銅合金板及びその製造方法 |
JP2016060958A (ja) * | 2014-09-19 | 2016-04-25 | Jx金属株式会社 | 電子部品用チタン銅 |
WO2020203576A1 (ja) * | 2019-03-29 | 2020-10-08 | 三菱マテリアル株式会社 | 銅合金板、めっき皮膜付銅合金板及びこれらの製造方法 |
Family Cites Families (4)
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JP2001181888A (ja) | 1999-12-17 | 2001-07-03 | Nippon Mining & Metals Co Ltd | コネクタ用めっき材料 |
JP3874621B2 (ja) | 2001-03-30 | 2007-01-31 | 株式会社神戸製鋼所 | 嵌合型接続端子用Snめっき銅合金材料及び嵌合型接続端子 |
JP5334648B2 (ja) | 2009-03-31 | 2013-11-06 | 株式会社神戸製鋼所 | 錫めっきの耐熱剥離性に優れた銅合金板 |
JP7388259B2 (ja) | 2020-03-13 | 2023-11-29 | トヨタ紡織株式会社 | 解除ハンドル |
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- 2022-08-31 DE DE112022004206.0T patent/DE112022004206T5/de active Pending
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- 2022-08-31 JP JP2023512395A patent/JP7315120B1/ja active Active
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WO2011086978A1 (ja) * | 2010-01-12 | 2011-07-21 | 三菱マテリアル株式会社 | 電気銅めっき用含リン銅アノード、その製造方法および電気銅めっき方法 |
WO2011122493A1 (ja) * | 2010-03-30 | 2011-10-06 | 三菱マテリアル株式会社 | 電気銅めっき用高純度銅アノード、その製造方法および電気銅めっき方法 |
JP2012122114A (ja) * | 2010-12-10 | 2012-06-28 | Mitsubishi Shindoh Co Ltd | 深絞り加工性及び耐疲労特性に優れたCu−Ni−Si系銅合金板及びその製造方法 |
JP2016060958A (ja) * | 2014-09-19 | 2016-04-25 | Jx金属株式会社 | 電子部品用チタン銅 |
WO2020203576A1 (ja) * | 2019-03-29 | 2020-10-08 | 三菱マテリアル株式会社 | 銅合金板、めっき皮膜付銅合金板及びこれらの製造方法 |
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JP7315120B1 (ja) | 2023-07-26 |
DE112022004206T5 (de) | 2024-07-25 |
JPWO2023033038A1 (ja) | 2023-03-09 |
CN117940613A (zh) | 2024-04-26 |
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