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WO2015075990A1 - Plaque d'alliage de cuivre, et composant électronique pour des applications de courant de forte intensité et composant électronique pour des applications de dissipation de chaleur chacun doté de cette dernière - Google Patents

Plaque d'alliage de cuivre, et composant électronique pour des applications de courant de forte intensité et composant électronique pour des applications de dissipation de chaleur chacun doté de cette dernière Download PDF

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Publication number
WO2015075990A1
WO2015075990A1 PCT/JP2014/072822 JP2014072822W WO2015075990A1 WO 2015075990 A1 WO2015075990 A1 WO 2015075990A1 JP 2014072822 W JP2014072822 W JP 2014072822W WO 2015075990 A1 WO2015075990 A1 WO 2015075990A1
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WO
WIPO (PCT)
Prior art keywords
copper alloy
electronic component
alloy plate
mass
mpa
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Ceased
Application number
PCT/JP2014/072822
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English (en)
Japanese (ja)
Inventor
明宏 柿谷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JX Nippon Mining and Metals Corp
Original Assignee
JX Nippon Mining and Metals Corp
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Filing date
Publication date
Application filed by JX Nippon Mining and Metals Corp filed Critical JX Nippon Mining and Metals Corp
Priority to KR1020167016227A priority Critical patent/KR101788497B1/ko
Priority to CN201480062948.8A priority patent/CN105765093A/zh
Publication of WO2015075990A1 publication Critical patent/WO2015075990A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc 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
    • H10W40/10—
    • H10W40/258—

Definitions

  • the present invention relates to a copper alloy plate excellent in heat dissipation, electrical conductivity, bending workability, and drawing workability, and more specifically for use in electronic parts such as terminals, connectors, relays, switches, sockets, bus bars, lead frames, especially smartphones.
  • the present invention relates to a copper alloy plate suitable for heat-dissipating parts used in personal computers and large current parts used in electric vehicles and hybrid vehicles.
  • austenitic stainless steel SUS304
  • pure aluminum and the like have been mainly used for heat dissipation components in electric and electronic devices such as smartphones, tablet PCs, and personal computers.
  • the heat-dissipating parts liquid crystal frame
  • the heat-dissipating parts liquid crystal frame
  • Austenitic stainless steel SUS304
  • has good bendability and drawability but has low thermal conductivity, and an expensive thermal conductive sheet or the like is used in combination to compensate for it. Therefore, the unit price of the heat dissipating component is increased.
  • pure aluminum and aluminum alloys have good bendability and drawability, but lack thermal conductivity and strength as a structure.
  • the cross-sectional area of the copper alloy in the current-carrying part tends to be small.
  • heat generation from the copper alloy when energized increases.
  • electronic components used in fast-growing electric vehicles and hybrid vehicles include components such as a battery connector that allow a very high current to flow, and heat generation of the copper alloy during energization is a problem. Therefore, the current-carrying material is required to have excellent conductivity so as to reduce the heat generation amount, and further, excellent bending workability and drawing workability are required so as to cope with downsizing and high functionality of parts.
  • thermal conductivity and conductivity are in a proportional relationship, and as an alloy having relatively high conductivity and strength, a material obtained by adding Zr or Ti to Cu is known.
  • materials having high electrical conductivity and relatively high strength include C15100 (0.1 mass% Zr-residual Cu), C15150 (0.02 mass% Zr-residual Cu), C18140 (0.1 mass% Zr-).
  • a conventional copper alloy with Cu or Zr added to Cu has high strength and heat conduction characteristics, but the required bending workability or drawing workability, depending on circumstances. Both were not met.
  • an object of the present invention is to provide a copper alloy plate having high strength and conductivity as well as excellent bending workability and drawing workability, a high-current electronic component and a heat dissipation electronic component including the copper alloy plate, Specifically, it is an object to improve the drawability of a Cu—Zr—Ti alloy that is inexpensive and excellent in conductivity and strength.
  • the present inventor improves bending workability and drawing workability in a Cu—Zr—Ti alloy by adjusting the metal structure using elongation as an index and controlling the orientation of crystal grains oriented on the rolling surface. I found out. And the following invention was completed against the background of the above knowledge.
  • the copper alloy sheet of the present invention contains one or two of Zr and Ti in total of 0.01 to 0.50% by mass, preferably 0.015 to 0.3% by mass, with the balance being copper and inevitable And having an electrical conductivity of 70% IACS or more and a 0.2% proof stress of 350 MPa or more, and 0.2% proof stress ⁇ (MPa) and elongation L (%) are ⁇ / L ⁇ 150 relationships are satisfied.
  • the X-ray diffraction integrated intensity of the ⁇ 220 ⁇ plane obtained in the thickness direction on the rolled surface using the X-ray diffraction method is I ⁇ 220 ⁇ , and the pure copper powder standard sample from the ⁇ 220 ⁇ plane is used.
  • the X-ray diffraction integrated intensity is I 0 ⁇ 220 ⁇ , it is preferable that I ⁇ 220 ⁇ / I 0 ⁇ 220 ⁇ ⁇ 4.0.
  • the ratio of the minimum bending radius (MBR) in the rolling parallel direction (GW direction) and the rolling perpendicular direction (BW direction) to the sheet thickness (t) in the W bending test is MBR / t.
  • MBR minimum bending radius
  • BW direction rolling perpendicular direction
  • t sheet thickness
  • the Erichsen value / plate thickness in the Erichsen test is given as 0.5 or more.
  • the electronic component for large current of the present invention comprises any one of the above copper alloy plates. Moreover, the electronic component for heat dissipation of this invention is provided with one of said copper alloy plates.
  • a copper alloy plate having high strength, high conductivity, excellent bending workability and drawing workability.
  • This copper alloy plate can be suitably used as a material for electronic parts such as terminals, connectors, switches, sockets, relays, bus bars, lead frames, heat sinks, etc.
  • the present invention relates to a copper alloy plate suitable for use in high-current parts used in automobiles, hybrid automobiles, and the like.
  • the copper alloy plate according to an embodiment of the present invention has a conductivity of 70% IACS or higher, a 0.2% proof stress of 350 MPa or higher, and a 0.2% proof stress / elongation ( ⁇ / L). 150 or less.
  • a copper alloy plate having such characteristics is suitable for use as an electronic component for heat dissipation.
  • the Cu—Zr—Ti alloy plate according to the embodiment of the present invention contains one or two of Zr and Ti in a total amount of 0.01 to 0.50% by mass.
  • the total content of is preferably 0.015 to 0.3% by mass, more preferably 0.02 to 0.20% by mass.
  • the total of one or two of Zr and Ti is less than 0.01% by mass, it becomes difficult to obtain a tensile strength of 350 MPa or more. If the total of one or two of Zr and Ti exceeds 0.5% by mass, it becomes difficult to produce an alloy due to hot rolling cracks or the like.
  • the amount added is preferably adjusted to 0.01 to 0.45 mass%, and when adding Ti, the amount added is adjusted to 0.01 to 0.20 mass%. It is preferable. If the addition amount is less than the lower limit value, the 0.2% proof stress is less than 350 MPa, and if the addition amount exceeds the upper limit value, conductivity and manufacturability may be deteriorated.
  • the Cu—Zr—Ti based alloy plate includes at least one of Ag, Co, Ni, Cr, Mn, Zn, Mg, Si, Fe, Sn and B in total. It can be contained at 2.0% by mass or less. However, if the amount added is too large, the electrical conductivity may be reduced to be less than 70% IACS or the manufacturability of the alloy may be deteriorated, so the amount added should be 1.0% by mass or less in total. Is preferable, and more preferably 0.5% by mass or less. Moreover, in order to acquire the effect by addition, it is preferable to make addition amount 0.001 mass% or more in total amount.
  • the thickness of the product that is, the plate thickness (t) is preferably 0.05 to 2.0 mm. If the thickness is too small, sufficient heat dissipation cannot be obtained, which is unsuitable as a material for heat dissipation electronic components. On the other hand, if the thickness is too large, bending and drawing are difficult. From such a viewpoint, a more preferable thickness is 0.08 to 1.5 mm. When the thickness is in the above range, it is possible to improve bending workability and drawing workability while suppressing heat storage.
  • the conductivity measured in accordance with JIS H0505 is 70% IACS or higher. If the electrical conductivity is 70% IACS or higher, the thermal conductivity is good and good heat dissipation can be ensured. More preferably, it is 75% IACS or more.
  • the 0.2% proof stress of the copper alloy plate is set to 350 MPa or more. According to this, it can be said that the copper alloy plate has a strength necessary as a material for the structural material.
  • (Elongation) More preferably, ⁇ / L ⁇ 150 so that the relationship of ⁇ / L ⁇ 150 is satisfied, where L (%) is the product elongation (El) and ⁇ (MPa) is 0.2% proof stress (YS).
  • L (%) is the product elongation (El)
  • ⁇ (MPa) is 0.2% proof stress (YS).
  • the 0.2% proof stress / elongation is 150 or less, it can be said that the required drawability is obtained.
  • the lower limit of ⁇ / L is preferably 30. If ⁇ / L is small, there is a concern that the 0.2% proof stress will not satisfy 350 MPa.
  • the upper limit value of the elongation L is not particularly limited, but usually when the value exceeds 15%, the strength decreases, and in some cases, the 0.2% proof stress may be less than 350 MPa. Therefore, in a preferred embodiment, the elongation L is 15% or less.
  • “Elongation” here refers to “breaking elongation” as defined in JIS Z2241, and “elongation” and “0.2% proof stress” refer to the rolling direction of the test piece in accordance with JIS Z2241. It shall be measured by a tensile test parallel to the direction.
  • the bending workability of this invention is performed by the W bending test (JIS H3130) using the strip-shaped test piece of width 10mm x length 30mm.
  • the specimen collection direction is a rolling parallel direction (GW) and a rolling perpendicular direction (BW), and evaluation is performed by a ratio MBR / t of a minimum bending radius MBR (Minimum Bend Radius) and a thickness t where no crack is generated.
  • the ratio (MBR / t) of the minimum bending radius (MBR) is preferably 2.0 or less from the viewpoint of ensuring good bendability. A more preferable range of MBR / t is 1.8 or less.
  • the ratio of the Erichsen value measured by the Erichsen test based on JIS Z2247 to the plate thickness is preferably 0.5 or more. If the Erichsen value / thickness is 0.5 or more, there is no practical problem as drawing workability. On the other hand, the Erichsen value / plate thickness is preferably 1.5 or less. This is because if it exceeds 1.5, the 0.2% proof stress may be less than 350 MPa. More preferably, the Erichsen value / plate thickness is in the range of 0.5 to 1.2.
  • the X-ray diffraction integrated intensity of the ⁇ 220 ⁇ plane obtained in the thickness direction on the rolled surface using the X-ray diffraction method is I ⁇ 220 ⁇
  • the X-ray diffraction integrated intensity from the ⁇ 220 ⁇ plane of the pure copper powder standard sample is I 0.
  • ⁇ 220 ⁇ is set and I ⁇ 220 ⁇ / I 0 ⁇ 220 ⁇ is 4.0 or more, drawing workability is improved.
  • I ⁇ 220 ⁇ / I 0 ⁇ 220 ⁇ is less than 4.0, since the texture development is small, the drawability is inferior.
  • I ⁇ 220 ⁇ / I 0 ⁇ 220 ⁇ is more preferably 4.0 to 7.0.
  • the pure copper powder standard sample is defined as a copper powder of 99.5% purity of 325 mesh (JIS Z8801).
  • melt electrolytic copper or the like as a pure copper raw material add Zr, Ti and other alloy elements as necessary, and cast into an ingot having a thickness of about 30 to 300 mm.
  • the ingot is made into a plate having a thickness of about 3 to 30 mm by hot rolling at 800 to 1000 ° C., for example, and then cold rolling and recrystallization annealing are repeated to finish to a predetermined product thickness by the final cold rolling.
  • the elongation after the final cold rolling is so low that it is less than 2%, but increases by subsequent strain relief annealing.
  • recrystallization annealing part or all of the rolled structure is recrystallized. Further, by annealing under appropriate conditions, Zr, Ti, etc. are precipitated, and the conductivity of the alloy is increased. In the recrystallization annealing before the final cold rolling, the average crystal grain size of the copper alloy sheet is adjusted to 50 ⁇ m or less. If the average crystal grain size is too large, it is difficult to adjust the 0.2% proof stress to 350 MPa or more.
  • the conditions for recrystallization annealing before final cold rolling are determined based on the target crystal grain size after annealing and the target product conductivity.
  • annealing may be performed using a batch furnace or a continuous annealing furnace with the furnace temperature set at 350 to 800 ° C.
  • the heating time may be appropriately adjusted within the range of 30 minutes to 30 hours at a furnace temperature of 350 to 600 ° C.
  • the heating time may be appropriately adjusted within the range of 5 seconds to 10 minutes at a furnace temperature of 450 to 800 ° C.
  • higher conductivity can be obtained with the same crystal grain size.
  • the material is repeatedly passed between a pair of rolling rolls to finish the target plate thickness.
  • the total workability of final cold rolling and the workability per pass are controlled.
  • the total processing degree R is 40 to 99%, preferably 45 to 98.5%, more preferably 50 to 98%. If the total workability R is too small, it is difficult to adjust the 0.2% proof stress to 350 MPa or more, and it is difficult to adjust I ⁇ 220 ⁇ / I 0 ⁇ 220 ⁇ to 4.0 or more. If the total workability R is too large, the edge of the rolled material may be broken. The degree of processing r per pass is 15% or more.
  • I ⁇ 220 ⁇ / I 0 ⁇ 220 ⁇ decreases, and if any path with a degree of processing r of less than 15% is included in all the paths, I ⁇ 220 ⁇ / I 0 ⁇ 220 ⁇ becomes difficult to adjust to 4.0 or more.
  • the strain relief annealing of the present invention is performed using a continuous annealing furnace capable of holding a copper alloy plate in a flat plate shape in the furnace.
  • a continuous annealing furnace capable of holding a copper alloy plate in a flat plate shape in the furnace.
  • the material is heated in a coiled state, so that the material undergoes plastic deformation during the heating, and the material is warped. Therefore, the batch furnace is not suitable for the strain relief annealing of the present invention.
  • the furnace temperature is 300 to 700 ° C., preferably 350 to 650 ° C.
  • the heating time is appropriately adjusted in the range of 5 seconds to 10 minutes, and 0.2% proof stress ( ⁇ ) after strain relief annealing. Is adjusted to a value 10 to 50 MPa lower, preferably 15 to 45 MPa lower than the 0.2% proof stress ( ⁇ 0 ) before strain relief annealing.
  • tension is applied to the material in a continuous annealing furnace, for example, in a direction parallel to the rolling direction, and the tension applied here is adjusted to 5 MPa or less, preferably 1 to 5 MPa, more preferably 2 to 4 MPa. If the tension is too large, it is difficult to adjust ⁇ / L to 150 or less. Further, the increase in elongation tends to be insufficient. On the other hand, if the tension is too small, the material in the passing plate of the annealing furnace may come into contact with the furnace wall, and the surface or edge of the material may be damaged.
  • One embodiment of the present invention provides a drawability by imparting a feature of ⁇ / L ⁇ 150 and a feature of I ⁇ 220 ⁇ / I 0 ⁇ 220 ⁇ ⁇ 4.0 to a Cu—Zr—Ti alloy.
  • One of the features is to improve the bending workability.
  • (1) For ⁇ / L ⁇ 150, a. In the strain relief annealing, ( ⁇ 0 ⁇ ) 10 to 50 MPa is adjusted. b. The furnace tension in the strain relief annealing is adjusted to 5 MPa or less.
  • the copper alloy plate manufactured as described above is processed into a copper product having various plate thicknesses, and is used as, for example, an electronic component for heat dissipation in an electric / electronic device such as a smartphone, a tablet PC, and a personal computer. Can do.
  • annealing before final cold rolling a batch furnace is used, the heating time is 5 hours, the furnace temperature is adjusted in the range of 300 to 700 ° C, and the crystal grain size and conductivity after annealing are adjusted. Changed.
  • the cross section perpendicular to the rolling direction was subjected to chemical corrosion after mirror polishing, and the average crystal grain size was determined by a cutting method (JIS H0501 (1999)).
  • the total workability and the workability per pass were controlled. Moreover, the 0.2% yield strength of the material after final cold rolling was calculated
  • strain relief annealing using a continuous annealing furnace the furnace temperature was 500 ° C., the heating time was adjusted between 1 second and 15 minutes, and the 0.2% proof stress after annealing was variously changed. In addition, various tensions were added to the material in the furnace. For some materials, strain relief annealing was omitted.
  • Tables 1 and 2 The production conditions of the examples are shown in Tables 1 and 2 for each invention example and comparative example. Here, a plurality of passes were carried out in the final cold rolling, but the minimum value in the degree of processing of each of these passes is shown.
  • Table 1 the notation “ ⁇ 5 ⁇ m” in the crystal grain size after the final recrystallization annealing indicates a case where only a part of the rolled structure is recrystallized. The following measurement was performed on the material in the process of manufacturing and the material after strain relief annealing.
  • the alloy element concentration of the material after strain relief annealing was analyzed by ICP-mass spectrometry.
  • sample No. 13B specified in JIS Z2241 was taken so that the tensile direction was parallel to the rolling direction, and pulled in parallel with the rolling direction in accordance with JIS Z2241. Tests were performed to determine 0.2% yield strength.
  • test piece was taken from the material after strain relief annealing so that the longitudinal direction of the test piece was parallel to the rolling direction, and the conductivity at 20 ° C. was measured by a four-terminal method in accordance with JIS H0505.
  • the X-ray diffraction integrated intensity of the ⁇ 220 ⁇ plane was measured in the thickness direction with respect to the surface of the material after strain relief annealing. Similarly, the X-ray diffraction integrated intensity of the ⁇ 220 ⁇ plane was measured for a pure copper powder standard sample.
  • RINT 2500 manufactured by Rigaku Corporation was used as the X-ray diffractometer, and measurement was performed with a Cu tube bulb at a tube voltage of 25 kV and a tube current of 20 mA.
  • Invention Examples 1 to 11 contain one or two of Zr and Ti in a total of 0.01 to 0.50% by mass, before the final cold rolling.
  • the crystal grain size is adjusted to 50 ⁇ m or less
  • the total workability is adjusted to 40 to 99%
  • the strain relief annealing the material is put into a continuous annealing furnace at a tension of 1 to 5 MPa. The 0.2% proof stress was reduced by 10 to 50 MPa through the plate.
  • the copper alloy sheets of Invention Examples 1 to 11 have a relationship of ⁇ / L ⁇ 150, a conductivity of 70% IACS or more, a 0.2% proof stress of 350 MPa or more, and an MBR / t ⁇ 2.0. W bendability could be achieved.
  • Comparative Examples 1 and 2 were not subjected to strain relief annealing, ⁇ / L exceeded 200, and the bendability and drawability were poor.
  • Comparative Examples 3 to 6 although strain relief annealing was performed, the material tension in the furnace exceeded 5 MPa, so ⁇ / L was 150 or more.
  • Comparative Example 5 in which the tension was particularly high, ⁇ / L was 200
  • the bendability and drawing workability of Comparative Examples 3 to 6 were poor.
  • Comparative Examples 7 and 8 the decrease in 0.2% proof stress during strain relief annealing was too small, and ( ⁇ 0 - ⁇ ) deviated from the range of 10 to 50 MPa. For this reason, ⁇ / L exceeded 150, and drawability and bendability were poor.
  • Comparative Example 9 since the strength decrease during strain relief annealing was large, the 0.2% proof stress after strain relief annealing was less than 350 MPa.
  • Comparative Example 10 since the total of one or two of Zr and Ti was less than 0.01% by mass, the 0.2% proof stress after strain relief annealing was less than 350 MPa. In Comparative Example 11, the total of one or two of Zr and Ti exceeded 0.5% by mass, so the conductivity was less than 70% IACS.
  • Comparative Example 12 the crystal grain size after recrystallization annealing before the final cold rolling exceeded 50 ⁇ m, and in Comparative Example 13, the total workability in the final cold rolling was less than 40%.
  • the 2% proof stress was less than 350 MPa.
  • a copper alloy plate having high strength and conductivity, and excellent drawing workability and bending workability, and a high-current electronic component and a heat dissipation electronic component provided with the copper alloy plate are provided. It is clear that it can be provided.

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Abstract

Une plaque d'alliage de cuivre selon la présente invention contient Zr et/ou Ti dans la quantité totale de 0,01 à 0,50 % en masse, avec le reste étant du cuivre et des impuretés inévitables. La plaque d'alliage de cuivre a une conductivité de 70 % IACS ou plus et une limite d'élasticité à 0,2 % de 350 MPa ou plus, la limite d'élasticité à 0,2 % (σ) (MPa) et l'allongement (L) (%) satisfont la relation représentée par la formule : σ/L ≤ 150.
PCT/JP2014/072822 2013-11-19 2014-08-29 Plaque d'alliage de cuivre, et composant électronique pour des applications de courant de forte intensité et composant électronique pour des applications de dissipation de chaleur chacun doté de cette dernière Ceased WO2015075990A1 (fr)

Priority Applications (2)

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KR1020167016227A KR101788497B1 (ko) 2013-11-19 2014-08-29 구리 합금판, 그리고 그것을 구비하는 대전류용 전자 부품 및 방열용 전자 부품
CN201480062948.8A CN105765093A (zh) 2013-11-19 2014-08-29 铜合金板、以及具备其的大电流用电子零件及散热用电子零件

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JP2013239197A JP5632063B1 (ja) 2013-11-19 2013-11-19 銅合金板、並びに、それを備える大電流用電子部品及び放熱用電子部品
JP2013-239197 2013-11-19

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JP6464742B2 (ja) * 2014-12-26 2019-02-06 三菱マテリアル株式会社 電子・電気機器用銅合金、電子・電気機器用銅合金薄板、電子・電気機器用部品、端子及びバスバー
JP6464741B2 (ja) * 2014-12-26 2019-02-06 三菱マテリアル株式会社 電子・電気機器用銅合金、電子・電気機器用銅合金薄板、電子・電気機器用部品、端子及びバスバー
JP6464740B2 (ja) * 2014-12-26 2019-02-06 三菱マテリアル株式会社 電子・電気機器用銅合金、電子・電気機器用銅合金薄板、電子・電気機器用部品、端子及びバスバー
JP6749121B2 (ja) * 2016-03-30 2020-09-02 Ｊｘ金属株式会社 強度及び導電性に優れる銅合金板
TWI674326B (zh) * 2018-11-19 2019-10-11 財團法人工業技術研究院 銅鋯合金散熱元件及銅鋯合金殼體的製造方法
CN110592421B (zh) * 2019-10-29 2020-07-07 吉林大学 铜合金、铜合金板材及其制备方法和应用
CN112281023B (zh) * 2020-11-23 2021-08-31 宁波博威合金材料股份有限公司 一种具有优异折弯性的铜合金材料及其制备方法和应用

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