WO2014064961A1 - 導電性及び応力緩和特性に優れる銅合金板 - Google Patents

導電性及び応力緩和特性に優れる銅合金板 Download PDF

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Publication number
WO2014064961A1
WO2014064961A1 PCT/JP2013/066875 JP2013066875W WO2014064961A1 WO 2014064961 A1 WO2014064961 A1 WO 2014064961A1 JP 2013066875 W JP2013066875 W JP 2013066875W WO 2014064961 A1 WO2014064961 A1 WO 2014064961A1
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copper alloy
less
alloy plate
mpa
alloy sheet
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PCT/JP2013/066875
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English (en)
French (fr)
Japanese (ja)
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波多野　隆紹
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Jx日鉱日石金属株式会社
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Priority to KR1020157008502A priority Critical patent/KR101716991B1/ko
Priority to CN201380054982.6A priority patent/CN104718302B/zh
Publication of WO2014064961A1 publication Critical patent/WO2014064961A1/ja

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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
    • 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
    • H01B1/026—Alloys based on copper

Definitions

  • the present invention relates to a copper alloy plate and electronic parts for energization or heat dissipation, and in particular, electronic parts such as terminals, connectors, relays, switches, sockets, bus bars, lead frames, heat sinks, etc. mounted on electric machines / electronic devices, automobiles and the like.
  • the present invention relates to a copper alloy plate used as a material for the above and an electronic component using the copper alloy plate.
  • copper alloys suitable for use in high current electronic parts such as high current connectors and terminals used in electric vehicles, hybrid cars, etc., or in heat dissipation electronic parts such as liquid crystal frames used in smartphones and tablet PCs.
  • the present invention relates to a plate and an electronic component using the copper alloy plate.
  • Parts for conducting electricity or heat such as terminals, connectors, switches, sockets, relays, bus bars, lead frames, heat sinks, etc., are built into automobiles, electrical equipment and electronic devices. Is used. Here, electrical conductivity and thermal conductivity are in a proportional relationship.
  • the copper alloy plate is deflected, and the contact force is obtained by the stress generated by this deflection.
  • the stress that is, the contact force is lowered due to the stress relaxation phenomenon, and the contact electric resistance is increased.
  • the copper alloy plate is required to be excellent in conductivity so that the amount of heat generation is reduced, and is also required to be excellent in stress relaxation characteristics so that the contact force does not decrease even if heat is generated.
  • a heat radiating part called a liquid crystal frame is used for a liquid crystal of a smartphone or a tablet PC.
  • a copper alloy plate for heat dissipation when stress relaxation characteristics are enhanced, creep deformation of the heat sink due to external force is suppressed, and the protection against liquid crystal components, IC chips, etc. disposed around the heat sink is improved. Etc. can be expected. For this reason, it is desired that the copper alloy plate for heat dissipation also has excellent stress relaxation characteristics.
  • Examples of materials having high electrical conductivity, relatively high strength, and good stress relaxation characteristics include C15100 (0.1 mass% Zr-residual Cu), C15150 (0.02 mass% Zr-residual Cu), C18140 (0 .1 mass% Zr-0.3 mass% Cr-0.02 mass% Si-residual Cu), C18145 (0.1 mass% Zr-0.2 mass% Cr-0.2 mass% Zn-residual Cu) C18070 (0.1% by mass Ti-0.3% by mass Cr-0.02% by mass Si-residual Cu), C18080 (0.06% by mass Ti-0.5% by mass Cr-0.1% by mass Ag) Alloys such as -0.08 mass% Fe-0.06 mass% Si-residual Cu) are registered in CDA (Copper Development Association).
  • a copper alloy in which Zr or Ti is added to Cu has relatively good stress relaxation characteristics, but the level of the stress relaxation characteristics is a large current. It is not always sufficient as a use of a component that supplies electricity or a component that dissipates a large amount of heat.
  • a component that supplies electricity or a component that dissipates a large amount of heat for example, in the copper alloy plate disclosed in Patent Document 1, 0.05 to 0.3 mass% of Zr is added, and Mg, Ti, Zn, Ga, Y, Nb, Mo, Ag, In, and Sn are included.
  • the stress relaxation characteristics were improved by adding 0.01 to 0.3% by mass of one or more of the above and further adjusting the crystal grain size after intermediate annealing to 20 to 100 ⁇ m.
  • the stress relaxation rate after holding for 1000 hours is at least 17.2%.
  • an object of the present invention is to provide a copper alloy plate having high strength, high conductivity, and excellent stress relaxation characteristics, and specifically, a Cu—Zr—Ti system having improved stress relaxation characteristics. It is an object to provide an alloy plate. Furthermore, another object of the present invention is to provide a method for producing the copper alloy plate and an electronic component suitable for high current use or heat dissipation use.
  • the present inventor combines high strength, high electrical conductivity, and excellent stress relaxation characteristics by including an appropriate amount of an element that improves stress relaxation characteristics in the copper alloy sheet. It has been found that a copper alloy sheet can be obtained.
  • the present invention completed on the basis of the above knowledge, in one aspect, contains 0.01 to 0.50 mass% of one or two of Zr and Ti in total, with the balance being made of copper and its inevitable impurities. , Having a conductivity of 70% IACS or more and a 0.2% proof stress of 330 MPa or more, and a stress relaxation rate of 15% or less after holding at 150 ° C. for 1000 hours, optionally, Ag, Fe, Co, A copper alloy plate containing 1.0% by mass or less of one or more of Ni, Cr, Mn, Zn, Mg, Si, P, Sn, and B.
  • the relationship between the spring limit value Kb (MPa) and the 0.2% yield strength ⁇ (MPa) is given by Kb ⁇ ( ⁇ 100).
  • the diffraction integrated intensities of the (111) plane and the (311) plane determined in the thickness direction on the rolled surface using an X-ray diffraction method are I (111) and I When (311) , I (111) / I (311) is 5.0 or less.
  • the present invention is a high-current electronic component using the copper alloy plate.
  • the ingot is hot-rolled at a temperature of 800 to 1000 ° C. to a thickness of 3 to 30 mm, and then cold rolling and recrystallization annealing are repeated.
  • a method for producing a copper alloy sheet for annealing (A) In the recrystallization annealing before the final cold rolling, the temperature inside the furnace is set to 350 to 800 ° C., and the average crystal grain size of the copper alloy sheet is adjusted to 50 ⁇ m or less.
  • a copper alloy plate having high strength, high conductivity, and excellent stress relaxation characteristics, a manufacturing method thereof, and an electronic component suitable for high current use or heat dissipation use.
  • This copper alloy can be suitably used as a material for electronic parts such as terminals, connectors, switches, sockets, relays, bus bars, lead frames, etc., and particularly dissipates the material or the large amount of heat of electronic parts that carry a large current.
  • the copper alloy plate according to the embodiment of the present invention has a conductivity of 70% IACS or more and a 0.2% proof stress of 330 MPa or more. If the electrical conductivity is 70% IACS or higher, it can be said that the amount of heat generated during energization is equivalent to that of pure copper. In addition, if the 0.2% proof stress is 330 MPa or more, it can be said that the material has a strength necessary for a material for a component that conducts a large current or a material for a component that dissipates a large amount of heat.
  • the stress relaxation rate of the copper alloy plate when the stress of 80% of 0.2% proof stress is applied and held at 150 ° C. for 1000 hours is 15 % Or less, more preferably 10% or less.
  • the stress relaxation rate of ordinary Cu-Zr-Ti alloys is about 25 to 35%, but by reducing this to 15% or less, the contact force decreases even when a large current is applied after processing the connector. Increase in contact electrical resistance is unlikely to occur, and creep deformation is unlikely to occur even if heat and external force are applied simultaneously after processing into a heat sink.
  • the copper alloy sheet according to the embodiment of the present invention contains one or two of Zr and Ti in total of 0.01 to 0.50% by mass, more preferably 0.02 to 0.20% by mass. . Thereby, strength and stress relaxation characteristics are improved as compared with a normal Cu—Zr—Ti alloy.
  • the total of one or two of Zr and Ti is less than 0.01% by mass, it becomes difficult to obtain a 0.2% proof stress of 330 MPa or more and a stress relaxation rate of 15% or less. 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.
  • the addition amount is less than the lower limit value, it is difficult to obtain the effect of improving the stress relaxation characteristics, and when the addition amount exceeds the upper limit value, conductivity and manufacturability may be deteriorated.
  • Cu-Zr-Ti alloy contains at least one of Ag, Fe, Co, Ni, Cr, Mn, Zn, Mg, Si, P, Sn and B in order to improve strength and heat resistance. Can be made. 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. Therefore, the amount added is preferably 1.0% by mass or less in total. Is 0.5 mass% or less. Moreover, in order to acquire the effect by addition, it is preferable to make addition amount into 0.001 mass% or more in total amount.
  • the stress relaxation characteristics of the copper alloy plate are improved.
  • the spring limit value of the product is Kb (MPa) and the 0.2% proof stress is ⁇ (MPa)
  • the relationship of Kb ⁇ ( ⁇ 100) is more preferable.
  • Kb ⁇ ( ⁇ 50) the stress relaxation characteristics are improved.
  • the stress relaxation rate exceeds 15%.
  • the upper limit value of Kb is not particularly restricted, but usually does not exceed ⁇ .
  • the stress relaxation properties of the copper alloy sheet are further improved.
  • the stress relaxation property is improved by adjusting I (111) / I (311) to 5.0 or less, preferably 2.0 or less on the rolled surface of the product.
  • I (111) and I (311) are diffraction integrated intensities of the (111) plane and the (311) plane, respectively, obtained in the thickness direction of the copper alloy plate using the X-ray diffraction method.
  • I (111) / I (311) exceeds 5.0, the stress relaxation rate exceeds 15%.
  • the lower limit of I (111) / I (311 ) is not limited in terms of the stress relaxation characteristics improved, I (111) / I ( 311) typically takes a value of more than 0.01.
  • the thickness of the product is preferably 0.1 to 2.0 mm. If the thickness is too thin, the cross-sectional area of the current-carrying part will decrease and heat generation will increase during energization, making it unsuitable as a material for connectors that carry large currents, and because it will deform with a slight external force, It is also unsuitable as a material. On the other hand, if the thickness is too thick, bending becomes difficult. From such a viewpoint, a more preferable thickness is 0.2 to 1.5 mm. When the thickness is in the above range, the bending workability can be improved while suppressing heat generation during energization.
  • the copper alloy plate according to the embodiment of the present invention can be suitably used for applications of electronic components such as terminals, connectors, relays, switches, sockets, bus bars, lead frames, heat sinks, in particular, electric vehicles, It is useful for applications of high-current electronic components such as high-current connectors and terminals used in hybrid vehicles and the like, or heat-dissipation electronic components such as liquid crystal frames used in smartphones and tablet PCs.
  • electronic components such as terminals, connectors, relays, switches, sockets, bus bars, lead frames, heat sinks, in particular, electric vehicles.
  • high-current electronic components such as high-current connectors and terminals used in hybrid vehicles and the like, or heat-dissipation electronic components such as liquid crystal frames used in smartphones and tablet PCs.
  • recrystallization annealing part or all of the rolled structure is recrystallized. Further, by annealing under appropriate conditions, Zr, Ti, etc. are precipitated, and the electrical 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 will be difficult to adjust the 0.2% yield strength of the product to 330 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.
  • a continuous annealing furnace 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 total workability of final cold rolling and the workability per pass are controlled.
  • the total processing degree R is preferably 25 to 99%. If R is too small, it becomes difficult to adjust the 0.2% proof stress to 330 MPa or more. When R is too large, the edge of the rolled material may be broken.
  • the processing degree r per pass is preferably 20% or less. If r is too large increases I (111) / I (311 ), the path that r is more than 20% among all paths include even one I a (111) / I (311) 5.0 It becomes difficult to adjust to the following.
  • the strain relief annealing of the present invention is performed using a continuous annealing furnace.
  • a continuous annealing furnace since the material is heated in a state of being wound in a coil shape, the material is deformed 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 temperature in the furnace is set to 300 to 700 ° C., the heating time is appropriately adjusted in the range of 5 seconds to 10 minutes, and the 0.2% proof stress ( ⁇ ) after the stress relief annealing is 0 before the stress relief annealing. Adjust to a value 10 to 50 MPa lower, preferably 15 to 45 MPa lower than 2% proof stress ( ⁇ 0 ). Thereby, Kb which was low in the final cold rolling is sufficiently increased. If ( ⁇ 0 ⁇ ) is too small or too large, Kb does not rise sufficiently, and it becomes difficult to obtain the relationship of Kb ⁇ ( ⁇ 100).
  • the tension applied to the material in the continuous annealing furnace is adjusted to 1 to 5 MPa, more preferably 1 to 4 MPa. If the tension is too large, it becomes difficult to adjust I (111) / I (311) to 5.0 or less. Further, the increase in Kb 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.
  • the copper alloy sheet of the present invention by adding the characteristics of Kb ⁇ ( ⁇ -100) and the characteristics of I (111) / I (311) ⁇ 5.0 to the Cu—Zr—Ti alloy, One of the features is to improve the stress relaxation characteristics.
  • Kb ⁇ ⁇ -100 a.
  • ( ⁇ 0 ⁇ ) 10 to 50 MPa
  • b Adjusting the furnace tension in the strain relief annealing to 5 MPa or less
  • I (111) / I (311) ⁇ 5.0 a.
  • the degree of processing per pass is adjusted to 20% or less
  • b Adjusting the furnace tension in the strain relief annealing to 5 MPa or less, It is preferable.
  • 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 350 to 700 ° C, and the crystal grain size and conductivity after annealing are adjusted. Changed.
  • the crystal grain size after annealing a 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. In some cases, strain relief annealing was not performed.
  • 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 (111) plane and (311) plane was measured in the thickness direction with respect to the surface of the material after strain relief annealing.
  • 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.
  • Table 1 shows the evaluation results. In the final cold rolling, a plurality of passes were performed, and the maximum value in the degree of processing of each pass was shown.
  • the notation of “ ⁇ 10 ⁇ m” in the crystal grain size after the final recrystallization annealing in Table 1 indicates that when all of the rolling structure is recrystallized and the average crystal grain size is less than 10 ⁇ m, and only a part of the rolling structure is used. Both cases of recrystallization are included.
  • the total concentration of Zr and Ti is adjusted to 0.01 to 0.50 mass%, and the crystal grain size is adjusted to 50 ⁇ m or less in the recrystallization annealing before the final cold rolling.
  • the total workability is adjusted to 25 to 99%, and the workability per pass is adjusted to 20% or less.
  • the strain relief annealing the material is passed through the continuous annealing furnace with a tension of 1 to 5 MPa. As a result, the 0.2% proof stress was reduced by 10 to 50 MPa.
  • Comparative Example 1 was not subjected to strain relief annealing, and the stress relaxation rate exceeded 30%.
  • Comparative Examples 2 to 4 although strain relief annealing was performed, the material tension in the furnace exceeded 5 MPa, so I (111) / I (311) exceeded 5.0, and the comparatively high tension In (3), ( ⁇ Kb) exceeded 100.
  • the stress relaxation rate exceeded 15%.
  • Comparative Examples 5 and 6 since the degree of work per pass in the final cold rolling exceeded 20%, I (111) / I (311) exceeded 5.0 and the stress relaxation rate exceeded 15%. .
  • Comparative Example 11 the total work degree in the final cold rolling was less than 25%, and in Comparative Example 12, the crystal grain size after recrystallization annealing before the final cold rolling exceeded 50 ⁇ m.
  • the 0.2% proof stress was less than 330 MPa.

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PCT/JP2013/066875 2012-10-22 2013-06-19 導電性及び応力緩和特性に優れる銅合金板 WO2014064961A1 (ja)

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KR1020157008502A KR101716991B1 (ko) 2012-10-22 2013-06-19 도전성 및 응력 완화 특성이 우수한 구리 합금판
CN201380054982.6A CN104718302B (zh) 2012-10-22 2013-06-19 导电性和应力缓和特性优异的铜合金板

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JP2012233005 2012-10-22
JP2012-233005 2012-10-22
JP2013090390A JP5470483B1 (ja) 2012-10-22 2013-04-23 導電性及び応力緩和特性に優れる銅合金板
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3950979A4 (en) * 2019-03-25 2022-08-10 JX Nippon Mining & Metals Corporation COPPER ALLOY PLATE, ELECTRONIC COMPONENT FOR ELECTRICITY PASSAGE, AND ELECTRONIC COMPONENT FOR HEAT DISSIPATION

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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
JP6749122B2 (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
JP6306632B2 (ja) * 2016-03-31 2018-04-04 Ｊｘ金属株式会社 電子材料用銅合金
JP6283048B2 (ja) * 2016-03-31 2018-02-21 株式会社神戸製鋼所 電気電子部品用銅合金条
TWI592946B (zh) * 2016-11-11 2017-07-21 Metal Ind Res & Dev Ct Copper alloy wire and its manufacturing method
JP7213086B2 (ja) * 2018-12-26 2023-01-26 Ｄｏｗａメタルテック株式会社 銅合金板材およびその製造方法

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WO2002012583A1 (en) * 2000-08-09 2002-02-14 Olin Corporation, A Corporation Of The Commonwealth Of Virginia Silver containing copper alloy
JP2004256902A (ja) * 2003-02-27 2004-09-16 Nikko Metal Manufacturing Co Ltd Ｃｕ−Ｃｒ−Ｚｒ合金およびその製造方法
JP2012012644A (ja) * 2010-06-30 2012-01-19 Hitachi Cable Ltd 銅合金の製造方法、及び銅合金
WO2012026611A1 (ja) * 2010-08-27 2012-03-01 古河電気工業株式会社 銅合金板材及びその製造方法
WO2012111567A1 (ja) * 2011-02-18 2012-08-23 三菱伸銅株式会社 Ｃｕ－Ｚｒ系銅合金板及びその製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3950979A4 (en) * 2019-03-25 2022-08-10 JX Nippon Mining & Metals Corporation COPPER ALLOY PLATE, ELECTRONIC COMPONENT FOR ELECTRICITY PASSAGE, AND ELECTRONIC COMPONENT FOR HEAT DISSIPATION

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TW201416463A (zh) 2014-05-01
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JP5470483B1 (ja) 2014-04-16
JP2014101574A (ja) 2014-06-05
KR20150047624A (ko) 2015-05-04
CN104718302A (zh) 2015-06-17
KR101716991B1 (ko) 2017-03-15

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