EP3460081B1 - Titane-cuivre pour composants électroniques - Google Patents

Titane-cuivre pour composants électroniques Download PDF

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Publication number
EP3460081B1
EP3460081B1 EP18196022.0A EP18196022A EP3460081B1 EP 3460081 B1 EP3460081 B1 EP 3460081B1 EP 18196022 A EP18196022 A EP 18196022A EP 3460081 B1 EP3460081 B1 EP 3460081B1
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EP
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Prior art keywords
titanium copper
crystal grain
cold rolling
mass
heat treatment
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EP18196022.0A
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German (de)
English (en)
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EP3460081A2 (fr
EP3460081A3 (fr
Inventor
Hiroyasu Horie
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JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
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Classifications

    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—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
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum

Definitions

  • the present invention is related to a titanium copper for electronic components which is suitable for electronic components, particularly connectors, battery terminals, jacks, relays, switches, autofocus camera modules, lead frames, and a method for manufacturing the titanium copper.
  • titanium copper has a relatively high strength and is excellent in stress relaxation characteristics among copper alloys. Therefore, titanium copper has been used for a long time as a material for signal terminals, whose strength is particularly required.
  • Titanium copper is an age hardening type copper alloy.
  • a supersaturated solid solution of Ti which is a solute atom
  • heat treatment for a relatively long time at a low temperature is performed from this state, a modulation structure, in which the Ti concentration in the parent phase fluctuates periodically, develops and results into improvement of strengthen, because of spinodal decomposition.
  • the problem is that the strength and the bending workability are contradictory properties. That is, if the strength is increased, the bending workability is impaired, and on the contrary, when emphasis is placed on the bending workability, the desired strength can not be obtained.
  • Patent Document 1 JP2013-100586A discloses a titanium copper comprising Ti of 1.5 to 5.0 mass%, and the rest consisting of copper and inevitable impurities, having a tensile strength of 800 MPa or more, wherein when an EBSD measurement is carried out parallel to the plate thickness direction at the central portion in the plate thickness direction which is a cross sectional position of 45 to 55% with respect to the thickness, and when the crystal orientation is analyzed, the area ratio of Cube orientation ⁇ 001 ⁇ ⁇ 100> Is 5% or more, the area ratio of Brass orientation ⁇ 110 ⁇ ⁇ 112> is 40% or less, and the area ratio of Copper orientation ⁇ 112 ⁇ ⁇ 111> is 20% or less. According to this disclosure, by controlling the crystal orientation inside the copper alloy plate in this way, it is possible to obtain sufficient bending workability for notch bending.
  • Patent Document 2 discloses a copper alloy sheet material containing 1.0 to 5.0 mass% of Ti and the rest consisting of copper and inevitable impurities, wherein in the crystal orientation analysis by EBSD measurement, the copper alloy sheet material is characterized in that the area ratio of the Cube orientation ⁇ 001 ⁇ ⁇ 100> is 5 to 50%. According to the disclosure, there is a correlation between the Cube orientation accumulation ratio and the bending workability, and by controlling this, a copper alloy sheet material having excellent bending workability and excellent strength can be obtained.
  • Patent Document 3 JP2015-190044A discloses that, at the stage before finish cold rolling, by controlling the ratio of the maximum side average crystal grain size / average grain size to be smaller than a certain level, and by reducing the number density of coarse second phase particles, the level of the bending workability of the copper alloy sheet material can be improved and variations can be reduced.
  • Patent Document 4 JP2004-052008A discloses a titanium copper alloy material comprising Ti of 1.0 to 5.0 mass% and the rest consisting of copper and inevitable impurities, characterized in that the value of the ratio of (the deviation of crystal grain size) / (the average crystal grain size) is 0.60 or less, and the mechanical properties such as bending workability and stress relaxation property of the titanium copper alloy material are uniform and good.
  • the inventors of the present invention conducted extensive research and discovered findings that, in order to improve the bending workability of titanium copper for electronic components to which beating process is applied, it is important to simultaneously control the coefficient of variation of crystal grain size when orientation difference of 5° or more is defined as a crystal grain boundary, and the area ratio of Cube orientation ⁇ 001 ⁇ ⁇ 100>.
  • the inventors also discovered finding that, to realize the control described above, when manufacturing a titanium copper by hot rolling an ingot of titanium copper, followed by a step of cold rolling and a final solution heat treatment, it is necessary to make the minimum working ratio per pass and the total working degree in the step of cold rolling within a certain range, while setting the rate of temperature rise and the heating temperature in the step of final solution heat treatment in a certain range.
  • the present invention is accomplished based on the above findings.
  • bending workability of titanium copper for electronic components can be improved, and a titanium copper for electronic components, which has excellent bending workability even when subjected to beating process, as well as a method for manufacturing the same, can be provided.
  • the Ti concentration is set to 2.0 to 4.5 mass%.
  • Ti is solidified in the Cu matrix by solution treatment, and fine precipitates are dispersed in the alloy by aging treatment, thereby increasing strength and conductivity.
  • the Ti concentration is less than 2.0 mass%, precipitation of precipitates becomes insufficient and desired strength cannot be obtained.
  • the Ti concentration exceeds 4.5% by mass, the processability is deteriorated, and the material is easily broken during rolling.
  • the preferable Ti concentration is 2.5 to 3.5 mass%.
  • one or more third element(s) selected from the group consisting of Fe, Co, Ni, Cr, Zn, Zr, P, B, Mo, V, Nb, Mn, Mg and Si can be contained, and thereby the strength can be further improved.
  • these third elements can be contained in a total amount of 0 to 0.5 mass%. In view of the balance between strength and workability, it is preferable to contain one or more of the above elements in a total amount of 0.1 to 0.4 mass%.
  • Zr, P, B, V, Mg and Si in an amount of 0.01 to 0.15 mass%, Fe, Co, Ni, Cr, Mo, Nb and Mn in an amount of 0.01 to 0.3 mass%, and Zn in an amount of 0.1 to 0.5 mass%, may be contained.
  • the titanium copper according to the present invention is characterized in that the relative variation in crystal grain size is small. This variation is evaluated using a coefficient of variation calculated from the average crystal grain size and standard deviation, particularly, from the formula: standard deviation / average crystal grain size x 100. The value of the coefficient of variation is set to 45% or less.
  • the coefficient of variation of crystal grain size is within the above range, variations in crystal grain size can be suppressed, and dislocation becomes uniform, and stress at the time of bending is dispersed, and improvement in bending workability can be expected.
  • the coefficient of variation of crystal grain size is preferably 43% or less, more preferably 41% or less, still more preferably 39% or less.
  • the average crystal grain size and the standard deviation are obtained by analyzing crystal orientation with the EBSD (Electron Back Scatter Diffraction) measurement on the rolled surface, using analysis software attached to EBSD (e.g. OIM Analysis provided by TSL Solutions Co., Ltd.), wherein the average crystal grain size and the standard deviation are calculated when an orientation difference of 5° or more is defined as a grain boundary.
  • EBSD Electro Back Scatter Diffraction
  • the following conditions are adopted as measurement conditions in the EBSD measurement.
  • the area ratio of the Cube orientation ⁇ 001 ⁇ ⁇ 100> is controlled to 5% or less. If the area ratio of the Cube orientation is 5% or less, in combination with the coefficient of variation of the crystal grain size described above, the bending workability of the titanium copper according to the present invention can be improved.
  • the reason for improving the bending workability of titanium copper is not clear, but it is presumed as follows. That is, when bending is applied, plastic deformation normally occurs, and strain accumulates in crystal grains. However, the Cube orientation is hard to be plastically deformed, and strain is hard to be introduced by bending processing. When the proportion of Cube orientation increases, the accumulation of strain becomes unbalanced and cracks are generated due to the locally accumulated strain. On the contrary, when the proportion of Cube orientation is small, the accumulation of strain becomes uniform and bending workability is improved. Furthermore, by reducing crystal grain size, the amount of strain accumulated in each crystal grain size is reduced, and the bendability is improved.
  • the Cube orientation refers to a state in which the (001) plane is oriented in the normal direction (ND) of the rolled surface and the (100) plane is in the rolling direction (RD) in crystal orientation analysis by EBSD measurement on the rolled surface. It is indicated by an index of ⁇ 001 ⁇ ⁇ 100>.
  • the titanium copper according to the present invention can have excellent bending workability.
  • the average roughness Ra of the outer peripheral surface of the bent portion is 1.0 ⁇ m or less.
  • the average roughness Ra is calculated according to JIS-B 0601 (2013). The fact that the average roughness of the bent portion is small even after the bending means that harmful cracks which may cause breakage are difficult to occur in the bent portion.
  • the average roughness Ra of the surface of the titanium copper according to the present invention before the bending test is 0.2 ⁇ m or less.
  • the working ratio which simulates a beating process, is based on the following equation.
  • T 0 is the thickness of the ingot before the cold rolling and T is the thickness of the ingot at the end of the cold rolling.
  • Working Ratio % T 0 ⁇ T / T 0 ⁇ 100
  • titanium copper it is preferable to control the average crystal grain size in the rolled surface within the range of 2 to 30 ⁇ m, more preferably in the range of 2 to 15 ⁇ m, and still more preferably in the range of 2 to 10 ⁇ m.
  • the average crystal grain size means the average crystal grain size obtained by analyzing the crystal orientation in the EBSD (Electron Back Scatter Diffraction) measurement on the rolled surface, using analysis software attached to EBSD (e.g. OIM Analysis provided by TSL Solutions Co., Ltd.), wherein the average crystal grain size is calculated when an orientation difference of 5° or more is defined as a grain boundary.
  • EBSD Electro Back Scatter Diffraction
  • 0.2% yield strength in a direction parallel to the rolling direction may be 800 MPa or more.
  • the 0.2% yield strength of titanium copper according to the present invention may be 850 MPa or more in a preferred embodiment, 900 MPa or more in a further preferred embodiment, and 950 MPa or more in a further preferred embodiment.
  • the upper limit of the 0.2% yield strength is not particularly restricted from the viewpoint of the strength intended by the present invention, but since it is troublesome and expensive, the 0.2% yield strength of titanium copper according to the present invention is generally 1300 MPa or less, typically 1200 MPa or less, more typically 1100 MPa or less.
  • the 0.2% yield strength in the direction parallel to the rolling direction is measured in accordance with JIS-Z 2241 (2011) (method for metal material tensile test).
  • the thickness can be 1.0 mm or less. In a typical embodiment, the thickness can be 0.02 to 0.8 mm, and in an more typical embodiment, the thickness can be 0.05 to 0.5 mm.
  • Titanium copper according to the present invention can be processed into various copper elongation products such as plates, strips, pipes, rods and wires.
  • the titanium copper according to the present invention is preferably used as a conductive material or a spring material in electronic components such as a switch, a connector, an autofocus camera module, a jack, a terminal (in particular, a battery terminal), a relay and the like, although its application is not limited.
  • electronic components can be used, for example, as in-vehicle parts or parts for electrical and electronic equipment.
  • Preparation of ingot by melting and casting is basically carried out in vacuum or in an inert gas atmosphere. If undissolved residues of the added element(s) is present during dissolution, it does not work effectively for improving the strength. Therefore, in order to eliminate undissolved residues, for third elements having a high melting point such as Fe or Cr, after add the element, it is necessary to sufficiently stir it, and to maintain a certain period of time. On the other hand, since Ti is relatively soluble in Cu, it may be added after dissolution of the third element(s).
  • the working ratio of the cold rolling is typically 30% or more.
  • annealing can then be carried out.
  • the annealing conditions are typically 900 ° C. and 1 to 5 minutes.
  • the cold rolling and the annealing can be repeated as necessary.
  • the reason for preliminarily performing solution heat treatment is to reduce the burden on the final solution treatment. That is, in the final solution heat treatment, since the second phase particles are already solutionized, heat treatment for solid solution of the second phase particles is not necessary, and it is only necessary to maintain this state and further cause recrystallization, so that a slight heat treatment is sufficient.
  • the first solution heat treatment may be performed at a heating temperature of 850 to 900 °C for 2 to 10 minutes. It is also preferable to make the heating rate and the cooling rate at that time as high as possible and to prevent precipitation of the second phase particles during this process. Note that the first solution heat treatment may not be performed.
  • the minimum working ratio per pass is less than 10%, it becomes difficult to control the area ratio of the Cube orientation of finally obtained titanium copper to 5% or less, whereas if the minimum working ratio per pass exceeds 30%, the material breaks and the production becomes difficult. From this viewpoint, the minimum working ratio per pass is preferably 13 to 27%, more preferably 16 to 24%.
  • the total working degree ⁇ is less than 1.0, it becomes difficult to control the coefficient of variation of the crystal grain size of finally obtained titanium copper to 45% or less, whereas when the total processing degree ⁇ is 3 .0 or more, it also becomes difficult to control the coefficient of variation of the crystal grain size of finally obtained titanium copper to 45% or less.
  • the total working degree ⁇ is preferably 1.3 to 2.7, more preferably 1.6 to 2.4.
  • the working ratio per pass can be obtained from the following equation.
  • T 0 is the thickness of the ingot before the cold rolling and T is the thickness of the ingot at the end of the cold rolling.
  • Working Ratio % T 0 ⁇ T / T 0 ⁇ 100
  • the heating temperature is set close to the solid solubility limit of the second phase particle composition.
  • the heating temperature (° C.) is set to (52 x X + 610) to (52 x X + 680).
  • the heating temperature is lower than 52 x X + 610, recrystallization becomes insufficient, and when the heating temperature exceeds 52 x X + 680, the crystal grain size becomes coarse, and the bending workability of finally obtained titanium copper is remarkably deteriorated.
  • heating time in the final solution heat treatment can suppress coarsening of crystal grains.
  • the heating time is 30 seconds to 10 minutes, and typically 1 minute to 8 minutes.
  • second phase particles are generated, as long as they are finely and uniformly dispersed, they are almost harmless to strength and bending workability.
  • coarse particles tend to grow further in the final aging treatment, so if second phase particles are generated during this period, they should be made as few as possible and should be made as small as possible.
  • the final solution heat treatment is followed by the final cold rolling.
  • the strength can be increased by the final cold rolling, in order to obtain bending workability as intended in the present invention, it is desirable set to the reduction ratio to 5 to 50%, preferably to 20 to 40%.
  • the final cold rolling is followed by aging treatment. It is preferable to heat at a material temperature of 300 to 500 °C for 1 to 50 hours, more preferably at a material temperature of 350 to 450 °C for 10 to 30 hours.
  • the aging treatment is preferably performed in an inert atmosphere such as Ar, N 2 , H 2 or the like in order to suppress the generation of the oxide film.
  • the method comprises:
  • steps such as grinding, polishing, shot-blast acid washing and the like for removing oxide scales on the surface can be appropriately performed between the above steps.
  • Alloys containing the alloy components shown in Table 1 and the rest consisting of copper and inevitable impurities were used as an experimental materials and effects of the alloy components, the production conditions for cold rolling and subsequent final solution heat treatment on the 0.2% yield strength, the coefficient of variation of crystal grain size, the area ratio of Cube orientation and the bending workability after rolling were investigated.
  • hot rolling was performed at 900 to 950 °C to obtain a hot rolled sheet having a thickness of 15 mm.
  • cold rolling and annealing were repeated to obtain strip thicknesses (0.3 to 3.3 mm), and a first solution heat treatment was performed on the stripes.
  • the conditions of the first solution heat treatment were heating at 850 °C for 10 minutes and then water cooling.
  • intermediate cold rolling was carried out under the conditions shown in Table 1, then inserted into an annealing furnace which is capable of rapid heating, and the final solution treatment was performed, followed by water cooling.
  • the heating conditions at this time were set as shown in Table 1.
  • JIS 13B test piece was prepared and the 0.2% yield strength in the direction parallel to the rolling direction was measured using a tensile tester according to the above measuring method.
  • a cold rolling with a working ratio of 10%, which simulates a beating process, was conducted, and subsequently a W bending test was performed in the Badway direction at r/t 1.0 in accordance with JIS-H 3130 (2012) after the cold rolling.
  • the outer peripheral surface of the bent portion of this test piece was observed.
  • the outer peripheral surface of the bent portion was photographed using a confocal microscope HD100 manufactured by Lasertec Corporation, and the average roughness Ra (according to JIS-B 0601: 2013) was measured using the attached software and compared.
  • the surface of the sample before bending was observed with a confocal microscope, irregularities were not confirmed, and the average roughness Ra was 0.2 ⁇ m or less in each case.
  • the coefficient of variation of the crystal grain size is 45% or less and the area ratio of the Cube orientation is 5% or less, so that the bending workability is excellent. Further, the average crystal grain size was 2 to 30 ⁇ m, and the 0.2% yield strength was 800 MPa or more.
  • Comparative Example 1 since the minimum working ratio per pass was too low, the area ratio of the Cube orientation was outside the range of the present invention, and the bending workability was inferior to the Examples.
  • Comparative Example 12 was produced in accordance with the invention according to Patent Document 4 described above.
  • the minimum working ratio per pass is low and the total working degree is also low.
  • the heating temperature is higher than the range of the present invention.
  • the area ratio of the Cube orientation exceeded the upper limit of the present invention, and the bending workability was inferior to the Examples.

Claims (6)

  1. Cuivre-titane, comprenant de 2,0 à 4,5% en masse de Ti, et au moins un élément choisi dans le groupe constitué par Fe, Co, Ni, Cr, Zn, Zr, P, B, Mo, V, Nb, Mn, Mg et Si pour un total de 0 à 0,5 % en masse en tant que troisième(s) élément(s), et le reste se composant de cuivre et d'impuretés inévitables,
    dans lequel dans une analyse d'orientation de cristaux par mesure EBSD sur la surface laminée, lorsqu'une différence d'orientation supérieure ou égale à 5° est définie comme une limite de grains cristallins, un coefficient de variation de taille de grains cristallins est inférieur ou égal à 45 %, et un rapport de surface d'orientation cubique {001} <100> est inférieur ou égal à 5 %.
  2. Cuivre-titane selon la revendication 1, dans lequel lorsqu'un test de flexion W a été réalisé dans la direction Badway à r/t = 1,0 conformément à la norme JIS-H 3130 (2012) après un laminage à froid avec un rapport de travail de 10 %, la rugosité moyenne Ra de la surface périphérique externe de la partie fléchie est inférieure ou égale à 1,0 µm.
  3. Cuivre-titane selon la revendication 1 ou 2, dans lequel dans l'analyse d'orientation cristalline par mesure EBSD sur la surface laminée, lorsqu'une différence d'orientation supérieure ou égale à 5° est définie comme une limite de grains cristallins, une taille de grains cristallins moyenne est de 2 à 30 µm.
  4. Cuivre-titane selon l'une quelconque des revendications 1 à 3, dans lequel lorsqu'un test de traction est réalisé selon la norme JIS-Z 2241 (2011), une limite d'élasticité à 0,2 % dans une direction parallèle à la direction de laminage est supérieure ou égale à 800 MPa.
  5. Composant électronique, comprenant le cuivre-titane selon l'une quelconque des revendications 1 à 4.
  6. Procédé de fabrication du cuivre-titane selon l'une quelconque des revendications 1 à 4, le procédé comprenant :
    une étape de laminage à chaud d'un lingot de cuivre-titane, le lingot comprenant de 2,0 à 4,5 % en masse de Ti, et au moins un élément choisi dans le groupe constitué par Fe, Co, Ni, Cr, Zn, Zr, P, B, Mo, V, Nb, Mn, Mg et Si pour un total de 0 à 0,5 % en masse en tant que troisième(s) élément(s), et le reste se composant de cuivre et d'impuretés inévitables ;
    une étape de laminage à froid ; et ensuite
    une étape de traitement thermique de la solution finale ;
    dans lequel dans l'étape de laminage à froid avant l'étape de traitement thermique de la solution finale, le rapport de travail minimal par passe est de 10 à 30 %, et lorsque le degré de travail total η est indiqué comme η = In {(épaisseur avant le laminage à froid) / (épaisseur après le laminage à froid)}, η est supérieur ou égal à 1,0 et inférieur à 3,0 ; et
    dans lequel dans l'étape de traitement thermique de la solution finale, lorsque la quantité d'addition (% en masse) de Ti est X, la température thermique finale (°C) est de (52 x X + 610) à (52 x X + 680), la vitesse d'augmentation de température de 400 °C à la température thermique finale est de 20 à 30 C/s, et la durée du traitement thermique de la solution finale est de 30 secondes à 10 minutes.
EP18196022.0A 2017-09-22 2018-09-21 Titane-cuivre pour composants électroniques Active EP3460081B1 (fr)

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JP2017182738A JP6310130B1 (ja) 2017-09-22 2017-09-22 電子部品用チタン銅

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EP3460081A2 EP3460081A2 (fr) 2019-03-27
EP3460081A3 EP3460081A3 (fr) 2019-05-15
EP3460081B1 true EP3460081B1 (fr) 2020-05-13

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JP3942505B2 (ja) 2002-07-16 2007-07-11 ヤマハメタニクス株式会社 チタン銅合金材及びその製造方法
JP4439003B2 (ja) * 2005-03-28 2010-03-24 日鉱金属株式会社 強度と曲げ加工性に優れたチタン銅合金及びその製造方法
EP2196548B1 (fr) * 2008-12-02 2012-05-16 Dowa Metaltech Co., Ltd. Matériau de feuille d'alliage de cuivre à base de Cu-Ti et son procédé de fabrication
US8097102B2 (en) * 2008-12-08 2012-01-17 Dowa Metaltech Co., Ltd. Cu-Ti-based copper alloy sheet material and method of manufacturing same
TWI539013B (zh) * 2010-08-27 2016-06-21 Furukawa Electric Co Ltd Copper alloy sheet and method of manufacturing the same
JP5261582B2 (ja) 2010-08-31 2013-08-14 古河電気工業株式会社 銅合金板材およびその製造方法
JP2013100586A (ja) 2011-11-09 2013-05-23 Jx Nippon Mining & Metals Corp チタン銅及びその製造方法
JP6196435B2 (ja) * 2012-10-02 2017-09-13 Ｊｘ金属株式会社 チタン銅及びその製造方法
JP6263333B2 (ja) * 2013-03-25 2018-01-17 Ｄｏｗａメタルテック株式会社 Ｃｕ−Ｔｉ系銅合金板材およびその製造方法並びに通電部品
JP5718443B1 (ja) * 2013-12-27 2015-05-13 Jx日鉱日石金属株式会社 電子部品用チタン銅
JP6368518B2 (ja) 2014-03-28 2018-08-01 Ｄｏｗａメタルテック株式会社 Ｃｕ−Ｔｉ系銅合金板材およびその製造方法並びに通電部品

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EP3460081A2 (fr) 2019-03-27
JP2019056166A (ja) 2019-04-11
EP3460081A3 (fr) 2019-05-15
RU2691007C1 (ru) 2019-06-07

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