EP2679341A1 - Kupferlegierungsplatte auf co-si-basis - Google Patents

Kupferlegierungsplatte auf co-si-basis Download PDF

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Publication number
EP2679341A1
EP2679341A1 EP12763618.1A EP12763618A EP2679341A1 EP 2679341 A1 EP2679341 A1 EP 2679341A1 EP 12763618 A EP12763618 A EP 12763618A EP 2679341 A1 EP2679341 A1 EP 2679341A1
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Prior art keywords
copper alloy
comparative example
alloy plate
based copper
buffing
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EP12763618.1A
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English (en)
French (fr)
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EP2679341B1 (de
EP2679341A4 (de
Inventor
Kazutaka Aoshima
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JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
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    • 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
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/10—Alloys based on copper with silicon as the next major constituent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12993—Surface feature [e.g., rough, mirror]

Definitions

  • the present invention relates to a Co-Si based copper alloy plate.
  • Co-Si based copper alloy As small sized electric and electronic equipment such as a connector is needed, a high strength Co-Si based copper alloy (Colson alloy) is developed. Since the Co-Si based Colson alloy is provided by producing a precipitate compound of Co and Si, it requires solution treatment at high temperature and aging. Therefore, a firm oxide film is formed on the surface, which degrades solder wettability. Also, the Colson alloy may be stress relief annealed after final rolling, which may further grow the oxide film. For this reason, acid pickling is conducted after a final heat treatment, and the oxide film is dissolved and further removed by buffing (hereinafter referred to as a "buffing with acid pickling").
  • a copper alloy material having improved solder wettability by specifying surface roughness Ra of 0.2 ⁇ m or less and Rt of 2 ⁇ m or less (Patent Literature 1).
  • a copper alloy material is developed by conducting acid pickling or degreasing before finish rolling, thereby improving the solder wettability (Patent Literature 2).
  • a peak position in a frequency distribution graph representing concave-convex components on the surface will appear at a plus side (at a convex component side) of a mean line for the roughness profile (0 position in the frequency distribution graph), and solder wettability and plating property will be improved.
  • the oxide film of the Co-Si based Colson alloy is quite firm, and is therefore not removed easily only by acid pickling.
  • only acid pickling is conducted after a heat treatment and no grinding is conducted, or no acid pickling and no grinding are conducted. It is considered that the oxide film on the surface of the material is not completely removed, and the pin holes may be easily generated. Accordingly, the present invention is made to solve the above-described problems.
  • An object thereof is to provide a Co-Si based copper alloy plate having excellent solder wettability and less pin holes generated when soldering.
  • a peak position in a frequency distribution graph representing concave-convex components on a surface in the direction transverse to rolling direction is at a minus side (a concave component side) of a mean line for the roughness profile.
  • the Co-Si based copper alloy plate may further comprising a total of 2.0% by mass or less of one or two or more selected from the group consisting of Mn, Fe, Mg, Ni, Cr, V, Nb, Mo, Zr, B, Ag, Be, Zn, Sn ,a misch metal and P.
  • Co-Si based copper alloy plate having excellent solder wettability and less pin holes generated when soldering.
  • % refers to % by mass, unless otherwise specified.
  • the surface roughness Ra is arithmetic mean roughness specified in JIS-B0601 (2001), and the surface roughness Rz is a maximum height roughness specified in the same JIS.
  • FIG. 1 shows an example of a production process of a Co-Si based copper alloy plate according to the present invention.
  • a copper alloy plate 2 after final heat treating is placed into a pickling tank 4 and is acid pickled, an oxide film is dissolved and thinned almost uniformly in a rolling direction (RD) and a direction transverse to rolling direction (TD). Therefore, a 60 degree specular gloss G(RD) in a rolling direction and a 60 degree specular gloss G(TD) in a direction transverse to rolling direction are almost same after pickling, and a difference ⁇ G(RD) - G(TD) ⁇ nearly equals to 0 (see Fig. 1(a) ).
  • a buff 6 is used to grind the copper alloy plate after acid pickling. Grinding mark flaws by buffing are left on a material.
  • the rolling direction (RD) that is a rotation direction of the buff 6, as the grinding on a surface of the material proceeds, the oxide film that is not completely dissolved upon acid pickling disappears from the surface of the material, the surface of the material becomes smooth and the G(RD) becomes great.
  • TD rolling direction
  • the grinding mark flaws by buffing are formed on the surface of the material in the TD direction. A degree of smooth is not largely changed, and the G(RD) is not largely changed. It results in ⁇ G(RD) - G(TD) ⁇ > 0.
  • the 60 degree specular gloss reflects a state of the surface of the material having a predetermined area.
  • the surface roughness (such as Ra) reflects a state of the surface of the material on a predetermined straight line. It is therefore considered that the 60 degree specular gloss reflects the state of a locally existing oxide film and foreign matters on the surface of the material better than the surface roughness.
  • the buff 6 is hollow cylindrical, and grinding grains are attached to the surface thereof.
  • a forward direction i.e., a threading direction of the copper alloy plate 2 (from left to right in Fig. 1 )
  • the grinding grains of the buff 6 grinds the surface of the copper alloy plate 2. Accordingly, a degree of the oxide film removal by the buffing process can be adjusted by a grain size (count) of respective grinding grains, a threading number of the copper alloy plate 2, a threading speed (line speed), a rotation number of the buff 6 and the like.
  • the surface roughness Ra (RD) in the rolling direction is preferably 0.07 ⁇ m or less. If the Ra (RD) is less than 0.07 ⁇ m, the zero cross time may be decreased.
  • a peak position in the frequency distribution graph of concave-convex components on the surface in the direction transverse to rolling direction can be specified.
  • the frequency distribution graph of the concave-convex components on the surface is identical with that described in Patent Literature 2, and is a plot where a horizontal axis represents a height from a mean line for the roughness profile and a vertical axis represents a frequency (measurement data numbers).
  • the horizontal axis is at 0.05 ⁇ m intervals (increments in between) for the mean line for the roughness profile and the measurement data numbers at the intervals are summed up as the frequency to generate the plot.
  • the "mean line for the roughness profile" is specified in JIS-B0601.
  • the frequency distribution graph is created as follows: (1) Firstly, "the height from a mean line for the roughness profile” is measured along a direction transverse to rolling direction of a sample. In other words, there are provided data of the height from the mean line for the roughness profile (hereinafter referred to as “measurement data” as appropriate) per surface position. The peak position or the like is determined from the resultant measurement data, and the measurement data is numerically treated to calculate Ra and Rz. (2) The height from the "mean line for the roughness profile” is delimited at 0.05 ⁇ m intervals. (3) The measurement data numbers (frequency) are counted at the 0.05 ⁇ m intervals.
  • measurement is made at an evaluation lenghth of 1.25 mm, a cut off value of 25 mm (in accordance with JIS-80601) and a scan speed of 0.1 mm/sec.
  • a surface roughness meter manufactured by Kosaka Laboratory Ltd. (Surfcorder SE3400) is used.
  • the measurement data numbers are 7500 points at an evaluation lenghth of 1.25 mm.
  • the method of measuring the peak position is identical with that described in Patent Literature 2.
  • the resultant measurement data is categorized as follows: When the height from "the mean line for the roughness profile" is more than 0, the data is categorized as upper (plus) components. When the height is less than 0, the data is categorized as lower (minus) components. Thus, the frequency distribution is plotted. The height ( ⁇ m) from “the mean line for the roughness profile” is replotted on the horizontal axis. The measurement data numbers are replotted as the frequency summed up at 0.05 ⁇ m intervals on the vertical axis. Thus, Figs. 2 and 3 are provided (corresponding to Fig. 3 in Patent Literature 2). In Figs.
  • the peak position of the frequency is a concave component (at a minus side), a convex component (at a plus side) or (0).
  • the "peak position” is determined as follows: Firstly, from the graphs (see Figs. 2 and 3 ) of a height from "the mean line for a frequency-roughness curve", the frequency having the highest value is denoted as P1 and the frequency having the second highest value is denoted as P2.
  • the peak position of the frequency is a concave component (at a minus side).
  • the peak position of the frequency is a convex component (at a plus side).
  • the peak position of the frequency is 0.
  • a line wherein the height from the mean line for the roughness profile being 0 ⁇ m is the mean line for the roughness profile.
  • Fig. 2 is a graph replotted by the frequency (%) on the vertical axis and the height ( ⁇ m) from the mean line for the roughness profile on the horizontal axis about actual measurement data in Example 4 described later.
  • Fig. 3 is a graph replotted by the frequency (%) on the vertical axis and the height ( ⁇ m) from the mean line for the roughness profile on the horizontal axis about actual measurement data in Example 18 described later.
  • the peak position in the frequency distribution graph of the concave-convex components on the surface is at the plus side (a convex component side) of the mean line for the roughness profile.
  • Fig. 3 the peak position in the frequency distribution graph of the concave-convex components on the surface is at the plus side (a convex component side) of the mean line for the roughness profile.
  • the peak position is at the minus side (a concave component side) of the mean line for the roughness profile.
  • a wetting property is good. The wetting property does not depend on the peak position.
  • the peak position is in the plus position because an acid pickling solution is changed upon acid pickling.
  • the method of measuring the surface roughness Ra, Rz is identical with that described in Patent Literature 2 and measurement is made at an evaluation length of 1.25 mm, a cut off value of 25 mm (in accordance with JIS-80601) and a scan speed of 0.1 mm/sec.
  • a surface roughness meter manufactured by Kosaka Laboratory Ltd. (Surfcorder SE3400) is used.
  • the measurement data numbers are 7500 points at an evaluation lenghth of 1.25 mm.
  • the surface roughness Ra, Rz is measured three times, which are averaged.
  • the composition includes Co: 0.5 to 3.0% by mass, Si: 0.1 to 1.0% by mass and the balance Cu with inevitable impurities. If the content of Co and Si is less than the above-defined range, precipitation by Co 2 Si is insufficient, and the strength cannot be enhanced. On the other hand, if the content of Co and Si exceeds the above-defined range, an electrical conductivity is degraded, and hot workability is also degraded.
  • the content of Co is preferably 1.5 to 2.5% by mass, more preferably 1.7 to 2.2% by mass.
  • the content of Si is preferably 0.3 to 0.7% by mass, more preferably 0.4 to 0.55% by mass.
  • a mass ratio of Co/Si is preferably 3.5 to 5.0, more preferably 3.8 to 4.6. Within the range of the mass ratio of Co/Si, Co 2 Si can be fully precipitated.
  • the composition further includes a total of 2.0% by mass or less of one or two or more selected from the group consisting of Mn, Mg, Ag, P, B, Zr, Fe, Ni, Cr, V, Nb, Mo, Be, Zn, Sn ,and a misch metal. If the total amount of the above element exceeds 2.0% by mass, the following advantages are saturated and the productivity is degraded. However, if the total amount of the element is less than 0.001% by mass, less advantages are provided.
  • the total amount of the element is preferably 0.001 to 2.0% by mass, more preferably 0.01 to 2.0% by mass, most preferably 0.04 to 2.0% by mass.
  • Ni, Cr, V, Nb, Mo, Be, Zn, Sn and a misch metal are complemented each other, and improve not only strength and electric conductivity, but also production properties such as a stress relaxation property, bending workability, a plating property, and manufacturability such as a hot workability by refining an ingot tissue.
  • elements that are not specifically described in the present specification may be added as long as the alloy of the present invention is not adversely affected.
  • an example of a method of producing the Co-Si based cooper alloy plate according to the present invention will be described.
  • an ingot including copper, alloy element(s) required, and inevitable impurities is hot rolled, mechanical finished, cold rolled, solution treated, and then aging treated to precipitate Co 2 Si.
  • the material is final cold rolled to have a predetermined thickness. If desired, a stress relief annealing may be further conducted.
  • the material is acid pickled and is promptly buffing.
  • Solution treatment may be conducted at any temperature within 700°C to 1000°C. Aging treatment may be conducted at 400°C to 650°C for 1 to 20 hours.
  • a reduction ratio of the final cold rolling is preferably 5% to 50%, more preferably 20% to 30%.
  • a crystal grain size of the alloy material according to the present invention is not especially limited, but is generally 3 to 20 ⁇ m.
  • a grain size of the precipitate is 5 nm to 10 ⁇ m.
  • the ingot having the composition shown in Table 1 was casted, was hot rolled at 900°C or more to have a thickness of 10 mm, mechanical finished to remove an oxidized scale on the surface, cold rolled, solution treated at a temperature within 700°C to 1000°C, and then aging treated at 400°C to 650°C for 1 to 20 hours.
  • the material was final cold rolled to have a predetermined thickness at a reduction ratio of 5 to 40%.
  • the material was stress relief annealed at 300 to 600°C for 0.05 to 3 hours.
  • the material was acid pickled and was promptly buffing under the conditions shown in Table 1.
  • An immersion time in the acid pickling was 60 to 180 seconds.
  • a buffing material used for the buffing was alumina grinding grains, and a nylon non-woven cloth containing the alumina. Buff materials having different buff texture roughnesses (counts of grinding grains) were used.
  • the count of the grinding grains represents the grinding grains by the number of mesh per inch, and is specified by JIS R6001. For example, when the count is 1000, an average size of the grinding grains will be 18 to 14.5 ⁇ m.
  • Respective samples thus obtained were evaluated for a variety of properties.
  • Arithmetic mean roughness Ra and a maximum height roughness Rz were measured in accordance with JIS B0601 (2001). Measurement was made in the rolling direction (RD) and the direction transverse to rolling direction (TD). The measurement was made at an evaluation length of 1.25 mm, a cut off value of 0.25 mm (in accordance with the JIS above described) and a scan speed of 0.1 mm/sec. A surface roughness meter manufactured by Kosaka Laboratory Ltd. (Surfcorder SE3400) was used. The measurement data numbers are 7500 points at an evaluation lenghth of 1.25 mm.
  • the measurement data in the direction transverse to rolling direction obtained in (1) was categorized into upper (plus) components and lower (minus) components from "the mean line for the roughness profile", a frequency distribution was plotted by delimiting the height from the "mean line for the roughness profile” at 0.05 ⁇ m intervals. From the measurement data, the frequency (%) was re-plotted on the vertical axis, and the height ( ⁇ m) from "the mean line for the roughness profile” was replotted on the horizontal axis. Thus, Figs. 2 and 3 were provided. In Figs.
  • 60 degree specular gloss was measured by using a gloss meter in accordance with JIS-Z8741 (trade name "PG-1M” manufactured by Nippon Denshoku Industries Co., Ltd.) at an entry angle of 60 degrees in the rolling direction RD and the direction transverse to rolling direction TD.
  • Fig. 2 is a graph replotted by the frequency (%) on the vertical axis and the height ( ⁇ m) from the mean line for the roughness profile on the horizontal axis about actual measurement data in Example 4.
  • Fig. 3 is a graph replotted by the frequency (%) on the vertical axis and the height ( ⁇ m) from the mean line for the roughness profile on the horizontal axis about actual measurement data in Example 18 described later.
  • a pin hole number refers to the number of the holes through which a base material (copper alloy material) is viewed without solder wetting. When the pin hole number increases, soldering may be imperfect.
  • the pin hole number was tested by acid pickling each sample having a width of 10 mm with a solution including 10% by mass of dilute sulfuric acid, immersing the sample into a solder bath at an immersion depth of 12 mm, an immersion speed of 25 mm/s and an immersion time of 10 sec, and pulling up the sample from the solder bath. Front and back sides of the sample were observed by an optical microscope (50 magnification), and the number of the pin holes through which the base material was visible was counted. If the number was not more than 5, the sample was determined as good.
  • solder test was conducted in accordance with JIS-C60068-2-54.
  • the solder bath composition was 60 wt% of tin and 40 wt% of lead.
  • An appropriate amount of a flux 25 wt% of rosin and 75 wt% of ethanol was added thereto.
  • a solder temperature was 235 ⁇ 3°C.
  • a zero cross time refers to a time until a wet stress value becomes zero. The shorter the zero cross time is, the more the solder wets.
  • the test was conducted by acid pickling the sample with a solution including 10% by mass of dilute sulfuric acid, and immersing the sample into the above-described solder bath at an immersion depth of 4 mm, an immersion speed of 25 mm/s, an immersion time of 10 sec and 235 ⁇ 3°C in accordance with JIS-C60068-2-54.
  • the zero cross time was determined by a meniscograph method. When the zero cross time was 2.0 sec or less, the solder wettability was determined as good.
  • Tables 1 to 3 show the results obtained.
  • methods A and B refer the buffing with acid pickling under the conditions described below.
  • the buffing with acid pickling was conducted before and after the finish rolling.
  • the acid pickling solution used for the buffing with acid pickling before the finish rolling was same as the acid pickling solution used for the buffing with acid pickling after the finish rolling discussed above.
  • Method A Number of buffing time of 1, threading speed of 40 m/min, buff texture roughnesses (grinding grains) of 1000 counts, and buff rotating number of 500 rpm
  • Method B Number of buffing time of 3, threading speed of 10 m/min, buff texture roughnesses (grinding grains) of 2000 counts, and buff rotating number of 1400 rpm
  • Example 1 No. Composition (wt%) Production process Buffing Co Si Other component Pretreatment before finish rolling Finish rolling Stress relief annealing Acid pickling Buffing Threading number Threading speed (m/min) Buff texture roughness (counts) Rotation number (/min)
  • Example 1 0.50 0.11 - ⁇ ⁇ ⁇ ⁇ 3 10 2000 1400
  • Example 2 1.00 0.23 - - ⁇ ⁇ ⁇ ⁇ 3 10 2000 1400
  • Example 3 1.50 0.40 - - ⁇ ⁇ ⁇ 3 10 2000 1400
  • Example 4 1.80 0.41 - - ⁇ ⁇ ⁇ ⁇ 3 10 2000 1400
  • Example 5 2.50 0.70 - - ⁇ ⁇ ⁇ ⁇ 3 10 2000 1400
  • Example 6 3.00 1.00 - - ⁇ ⁇ ⁇ ⁇ 3 10 2000 1400
  • Example 7 1.50 0.40 - - ⁇ ⁇ ⁇ 2 10 2000 1400
  • Example 8 1.50 0.40 - - ⁇ ⁇ ⁇ ⁇
  • the buffing with acid pickling in each Example was conducted under the conditions: grinding grains of 2000 counts or more, threading time of two or more, threading speed of 10 mpm or less, and rotating number of 1200 rpm or more. It should be appreciated that these optimum ranges are changed depending on a production apparatus.
  • a cause of degradation may be that when the buffing with acid pickling was conducted in Comparative Examples 1, 2, 15, 17 and 19, the threading speed exceeded 20 mpm.
  • the cause of degradation may be that in Comparative Examples 3, 5, 8 and 20 the threading time was less than two.
  • the buffing with acid pickling was conducted using the above-described method A after the final rolling.
  • the cause of degradation may be that in Comparative Example 13 no buffing was conducted although acid pickling was conducted.
  • Comparative Examples 6 and 7 where the count of the grinding grains used in the buffing with acid pickling was 4000, the grinding grains were too fine to grind, and it is thus considered that Ra(RD) is not so decreased.
  • the cause of degradation may be that, in Comparative Examples 11 and 12, the rotating number in the buffing with acid pickling was less than 1200 rpm.
  • the grinding grains were coarse and the surface after the buffing with acid pickling became roughened, ⁇ (60 degree specular gloss G(RD) in a rolling direction) - (60 degree specular gloss G(TD) in a direction transverse to rolling direction) ⁇ ⁇ 90%, the pin holes are increased and the zero cross time was bad. It is considered that, since the count of the grinding grains used in the buffing with acid pickling was 500, the grinding grains were too coarse.
  • the cause of degradation may be that, in Comparative Examples 4, 14, 16, 18 and 21 where no buffing with acid pickling was conducted after the final rolling, the oxide film on the surface and the foreign matters pushed were not removed and the rolled surface was left as it is.
  • Comparative Example 21 was similar to each Example except that the roughness of the mill rolls of the final rolling was finer.
  • Comparative Examples 16 and 18 the treatment (acid pickling or degreasing) was conducted before the finish rolling and no buffing with acid pickling was conducted. As a result, the peak position was at the plus side (at the convex component side) of the mean line for the roughness profile (0 position in the frequency distribution graph representing the concave-convex components on the surface). In other words, these Comparative Examples show the copper alloy plate described in Patent Literature 2. In Comparative Examples 4, 13, 16 and 21, the zero cross time exceeded 2.0 sec and the solder wettability was degraded. It is considered that, since no acid pickling and no buffing were conducted, the oxide film remained on the surface of the metal (Comparative Example 16 corresponds to the conditions described in Patent Literature 2).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Conductive Materials (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
EP12763618.1A 2011-03-28 2012-03-07 KUPFERLEGIERUNGSPLATTE, DIE Co UND Si ENTHÄLT Active EP2679341B1 (de)

Applications Claiming Priority (2)

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JP2011070183A JP4831552B1 (ja) 2011-03-28 2011-03-28 Ｃｏ−Ｓｉ系銅合金板
PCT/JP2012/055830 WO2012132805A1 (ja) 2011-03-28 2012-03-07 Co-Si系銅合金板

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EP2679341A1 true EP2679341A1 (de) 2014-01-01
EP2679341A4 EP2679341A4 (de) 2014-12-24
EP2679341B1 EP2679341B1 (de) 2016-07-27

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US (1) US20140065441A1 (de)
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JP (1) JP4831552B1 (de)
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CN (1) CN103429388B (de)
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CN112695219A (zh) * 2020-12-11 2021-04-23 中南大学 一种提高熔炼铸造Cu-Cr-Nb合金强度和导电率的方法

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JP6126791B2 (ja) 2012-04-24 2017-05-10 Ｊｘ金属株式会社 Ｃｕ−Ｎｉ−Ｓｉ系銅合金
TWI612691B (zh) * 2013-09-02 2018-01-21 Furukawa Electric Co Ltd 用於光半導體裝置之引線框架用之基體及其製造方法、用有此之用於光半導體裝置之引線框架及其製造方法、及光半導體裝置
KR20160117210A (ko) 2015-03-30 2016-10-10 제이엑스금속주식회사 Cu-Ni-Si 계 압연 구리 합금 및 그 제조 방법
JP6177299B2 (ja) * 2015-11-04 2017-08-09 Ｊｘ金属株式会社 メタルマスク材料及びメタルマスク
US20170208680A1 (en) * 2016-01-15 2017-07-20 Jx Nippon Mining & Metals Corporation Copper Foil, Copper-Clad Laminate Board, Method For Producing Printed Wiring Board, Method For Producing Electronic Apparauts, Method For Producing Transmission Channel, And Method For Producing Antenna
JP2019065361A (ja) * 2017-10-03 2019-04-25 Ｊｘ金属株式会社 Ｃｕ−Ｎｉ−Ｓｎ系銅合金箔、伸銅品、電子機器部品およびオートフォーカスカメラモジュール
JP7169149B2 (ja) * 2017-10-20 2022-11-10 住友化学株式会社 非水電解液二次電池用セパレータ
JP7296757B2 (ja) * 2019-03-28 2023-06-23 Ｊｘ金属株式会社 銅合金、伸銅品及び電子機器部品

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KR20130122667A (ko) 2013-11-07
US20140065441A1 (en) 2014-03-06
JP4831552B1 (ja) 2011-12-07
EP2679341B1 (de) 2016-07-27
KR101569262B1 (ko) 2015-11-13
EP2679341A4 (de) 2014-12-24
CN103429388A (zh) 2013-12-04

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