WO2011068135A1 - Feuille d'alliage de cuivre et son procédé de fabrication - Google Patents

Feuille d'alliage de cuivre et son procédé de fabrication Download PDF

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WO2011068135A1
WO2011068135A1 PCT/JP2010/071518 JP2010071518W WO2011068135A1 WO 2011068135 A1 WO2011068135 A1 WO 2011068135A1 JP 2010071518 W JP2010071518 W JP 2010071518W WO 2011068135 A1 WO2011068135 A1 WO 2011068135A1
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Prior art keywords
orientation
copper alloy
heat treatment
alloy sheet
rolling
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PCT/JP2010/071518
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English (en)
Japanese (ja)
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洋 金子
浩二 佐藤
立彦 江口
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古河電気工業株式会社
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Application filed by 古河電気工業株式会社 filed Critical 古河電気工業株式会社
Priority to JP2011513178A priority Critical patent/JP4885332B2/ja
Priority to KR1020127012528A priority patent/KR101419147B1/ko
Priority to EP10834585.1A priority patent/EP2508635B1/fr
Priority to CN201080051567.1A priority patent/CN102695811B/zh
Publication of WO2011068135A1 publication Critical patent/WO2011068135A1/fr
Priority to US13/486,903 priority patent/US20120267013A1/en

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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
    • 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
    • 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

Definitions

  • the present invention relates to a copper alloy sheet material and a method of manufacturing the same, and more particularly to a copper alloy sheet material applied to lead frames, connectors, terminal materials, relays, switches, sockets, etc. for automotive parts and electric / electronic devices .
  • Characteristic items required for copper alloy sheet materials used for applications such as lead frames for automotive parts and for electric and electronic devices, connectors, terminal materials, relays, switches, sockets, etc. include, for example, conductivity, proof stress (yield Stress, tensile strength, bending workability, stress relaxation resistance, etc.
  • proof stress yield Stress
  • tensile strength tensile strength
  • bending workability stress relaxation resistance
  • the level of these required characteristics is increasing. For this reason, the following changes are mentioned to the condition where the copper alloy board material in recent years is used.
  • the miniaturization of terminals and contact parts is progressing.
  • Patent Document 1 in the case of a crystal orientation in which the crystal grain diameter and the X-ray diffraction intensity from the ⁇ 311 ⁇ , ⁇ 220 ⁇ , and ⁇ 200 ⁇ planes satisfy a certain condition in the Cu—Ni—Si copper alloy. , It has been found that bending workability is excellent. Further, in Patent Document 2, in the case of a crystal orientation that satisfies the condition that X-ray diffraction intensity from ⁇ 200 ⁇ and ⁇ 220 ⁇ planes is excellent in Cu-Ni-Si copper alloy, bending workability is excellent. Has been found.
  • Patent Document 3 it is found that in a Cu—Ni—Si-based copper alloy, bending workability is excellent by control of the proportion of Cube orientation ⁇ 100 ⁇ ⁇ 001>.
  • Patent Documents 4 to 8 also propose materials excellent in bending workability defined by X-ray diffraction intensities of various atomic planes.
  • the X-ray diffraction intensity from the ⁇ 200 ⁇ plane is from the ⁇ 111 ⁇ , ⁇ 200 ⁇ , ⁇ 220 ⁇ and ⁇ 311 ⁇ planes. It has been found that bending workability is excellent in the case of a crystal orientation that satisfies a certain condition for X-ray diffraction intensity.
  • Patent Document 5 it is seen that in a Cu-Ni-Si based copper alloy, bending workability is excellent in the case of a crystal orientation satisfying the condition that X-ray diffraction strength from the ⁇ 420 ⁇ plane and the ⁇ 220 ⁇ plane is present. It has been issued.
  • Patent Document 6 it is found that, in a Cu-Ni-Si-based copper alloy, in the case of a crystal orientation which satisfies a certain condition regarding the ⁇ 123 ⁇ ⁇ 412> orientation, bending workability is excellent.
  • Patent Document 7 in a Cu-Ni-Si based copper alloy, in the case of a crystal orientation that satisfies a condition that X-ray diffraction intensity from the ⁇ 111 ⁇ plane, ⁇ 311 ⁇ plane and ⁇ 220 ⁇ plane is satisfied, Bad Way ( It is found that the bending workability of the following item) is excellent. Further, in Patent Document 8, bending is performed in the case of a crystal orientation that satisfies the condition that X-ray diffraction intensity from the ⁇ 200 ⁇ plane, ⁇ 311 ⁇ plane and ⁇ 220 ⁇ plane is satisfied in the Cu—Ni—Si based copper alloy. It has been found that the processability is excellent.
  • the prescription by the X-ray diffraction intensity in patent documents 1, 2, 4, 5, 7, and 8 prescribes accumulation of a specific crystal plane to a plate surface direction (rolling normal direction, ND).
  • Patent Document 1 or Patent Document 2 is based on the measurement of crystal orientation by X-ray diffraction from a specific crystal plane, and it is very useful in the distribution of crystal orientation having a certain spread. It relates only to some specific aspects. Moreover, only the crystal plane in the plate surface direction (ND) is measured, and it can not be controlled which crystal plane is in the rolling direction (RD) or the plate width direction (TD). Therefore, it was still an insufficient method to completely control bending workability. Moreover, in the invention described in Patent Document 3, although the effectiveness of the Cube orientation is pointed out, other crystal orientation components are not controlled, and there are cases where improvement in bending workability is insufficient. The Further, in Patent Documents 4 to 8, studies have only been made to measure and control the above-mentioned specific crystal planes or orientations, respectively, and as in Patent Documents 1 to 3, there are cases where improvement in bending workability is insufficient. The
  • the present inventors repeated various studies, researched on copper alloys suitable for electric and electronic component applications, and characterized by EBSD method, BR orientation, RD-rotated-cube orientation (hereinafter also referred to as RDW orientation) It is found that the crack at the time of bending is suppressed by increasing the and cube orientation and reducing the copper orientation, the S orientation and the brass orientation, and further, the area ratio of the texture orientation component of each orientation It has been found that bending workability can be significantly improved by setting the ratio of In addition, it has been found that by using a specific additive element in the present alloy system, the strength and the stress relaxation resistance can be improved without impairing the conductivity and the bending workability. The present invention has been made based on these findings.
  • the present invention provides the following solutions.
  • BR orientation ⁇ 3 62 2 ⁇ ⁇ 8 5 3> In crystal orientation analysis in EBSD (Electron Back Scatter Diffraction: electron backscattering diffraction) measurement, BR orientation ⁇ 3 62 2 ⁇ ⁇ 8 5 3>, RD-Roted-Cube orientation ⁇ 0 1 2 ⁇ ⁇ 1 0 0 >, Cube orientation ⁇ 1 0 0 ⁇ ⁇ 0 0 1>, Copper orientation ⁇ 1 2 1 ⁇ ⁇ 1 1 1>, S orientation ⁇ 2 3 1 ⁇ ⁇ 3 4 6>, Brass orientation ⁇ 1 1 0 ⁇ ⁇ 1
  • a copper alloy sheet material characterized in that R is defined as 1 or more, the proof stress is 500 MPa or
  • the sheet After two passes or more of hot rolling with a pass working ratio of 25% or more, the sheet is cooled to (P-30) ° C or less, and at a temperature of 400 ° C or more at (P-30) ° C or less Manufacture of a copper alloy sheet material characterized by performing two or more passes of 25% or less hot rolling Method.
  • (7) After the aging precipitation heat treatment [Step 10], cold rolling [Step 11] and temper annealing [Step 12] are performed in this order, and the copper alloy sheet according to the item (6) is Production method.
  • the copper alloy sheet material of the present invention is excellent in bending workability and has excellent strength, and lead frames, connectors, terminal materials, etc. for electric and electronic devices, connectors, terminal materials, relays, switches, etc. Preferred. Further, the method for producing a copper alloy sheet material of the present invention is excellent in the above-mentioned bending processability and has excellent strength, and lead frame, connector, terminal material for electric and electronic devices, etc. It is suitable as a method of manufacturing a copper alloy sheet suitable for terminal materials, relays, switches and the like.
  • copper alloy material means one obtained by processing a copper alloy material into a predetermined shape (e.g., plate, strip, foil, bar, wire, etc.).
  • a plate material refers to a plate having a specific thickness, being stable in shape and having a spread in the surface direction, and in a broad sense, it includes a bar material.
  • material surface layer means “plate surface layer”
  • depth position of material means “position in the plate thickness direction”.
  • the thickness of the plate is not particularly limited, but is preferably 8 to 800 ⁇ m, more preferably 50 to 70 ⁇ m, in consideration of the fact that the effects of the present invention are more apparent and suitable for practical applications.
  • the copper alloy sheet material of the present invention defines its characteristic by the accumulation ratio of atomic planes in a predetermined direction of the rolled sheet, it is sufficient if it has such a characteristic as a copper alloy sheet material. That is, the shape of the copper alloy sheet is not limited to the sheet and the strip, and in the present invention, the pipe can be interpreted as a sheet and handled.
  • the present inventors investigated in detail the metallographic structure of the material after bending deformation in order to clarify the cause of cracking during bending of a copper alloy sheet. As a result, it was observed that the substrate material was not uniformly deformed, but the deformation was concentrated only in a region of a specific crystal orientation, and non-uniform deformation progressed. Then, it was found that wrinkles with a depth of several microns and fine cracks were generated on the surface of the base material after bending due to the uneven deformation.
  • R defined as + [B] is 1 or more.
  • they are 1.1 or more, More preferably, they are 1.2 or more and 6 or less.
  • the material is taken along a rectangular coordinate system in which the rolling direction (RD) of the material is the X axis, the sheet width direction (TD) is the Y axis, and the rolling normal direction (ND) is the Z axis.
  • (Hkl) [uvw] using the index (hkl) of the crystal plane in which each region is perpendicular to the Z axis (parallel to the rolling plane) and the index of the crystal orientation [uvw] parallel to the X axis Show in the form.
  • equivalent orientations under the cubic symmetry of copper alloys such as (1 32) [6-4 3] and (2 3 1) [3-4 6] etc.
  • the six types of orientations in the present invention are indicated by the indices as described above.
  • EBSD Electron Back Scatter Diffraction
  • Electron Back Scatter Diffraction Electron Back Scatter Diffraction
  • Kikuchi pattern a reflection electron Kikuchi line diffraction (Kikuchi pattern) generated when a sample is irradiated with an electron beam in a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • a sample area of 500 ⁇ m square containing 200 or more crystal grains was scanned at 0.5 ⁇ m steps to analyze the orientation.
  • a crystal grain having each texture orientation component of the orientation of the BR, RD-Roted-Cube (RDW), Cube (W), Copper (C), S and Brass (B) and its atomic plane The area is defined as to whether it falls within a predetermined deviation angle described below.
  • the deviation angle from the ideal orientation indicated by the above index (i) the crystal orientation of each measurement point and (ii) any one of BR, RDW, Cube, Copper, S, and Brass as the ideal orientation to be targeted
  • the rotation angle was calculated around the common rotation axis in (i) and (ii), and the deviation angle was used.
  • Information obtained in orientation analysis by EBSD includes orientation information up to a depth of several tens of nm at which an electron beam penetrates into a sample, but is sufficiently small relative to the width being measured. It described as an area ratio.
  • the measurement in order to obtain a clear Kikuchi line diffraction image, it is preferable to perform the measurement after mirror polishing of the substrate surface using abrasive grains of colloidal silica after mechanical polishing. Moreover, the measurement was performed from the plate surface.
  • ⁇ Ni, Co, Si Copper or a copper alloy is used as the connector material of the present invention.
  • copper alloys such as phosphor bronze, brass, nickel-white, beryllium copper, Corson alloys (Cu-Ni-Si), etc., which have the electrical conductivity, mechanical strength and heat resistance required for connectors Is preferred.
  • a precipitation type alloy containing pure copper material, beryllium copper, or Corson alloy is preferable.
  • Precipitation type copper alloys are preferred. This is because, in a solid solution type alloy such as phosphor bronze or brass, a micro area having a Cube orientation in a cold-rolled material, which becomes a nucleus of Cube orientation grain growth in grain growth during heat treatment, is reduced. This is because shear bands easily develop during cold rolling in a system with low stacking fault energy such as phosphor bronze and brass.
  • Ni—Si and Co are controlled by controlling the respective addition amounts of nickel (Ni), cobalt (Co) and silicon (Si) which are the first additive element group to be added to copper (Cu).
  • the strength of the copper alloy can be improved by precipitating a compound of -Si and Ni-Co-Si.
  • the addition amount thereof is preferably 0.5 to 5.0 mass%, more preferably 0.6 to 4.5 mass%, more preferably 0.8 to 5.0 mass% in total of any one or two of Ni and Co. It is 4.0 mass%.
  • the addition amount of Ni is preferably 1.5 to 4.2 mass%, more preferably 1.8 to 3.9 mass%, while the addition amount of Co is preferably 0.3 to 1.8 mass%, more preferably Is 0.5 to 1.5 mass%.
  • Co is a rare element, and in order to increase the solution temperature by the addition amount, it is preferable not to add Co unless it is necessary to significantly increase the conductivity depending on the application.
  • the effects of the additional elements for improving the characteristics (secondary characteristics) such as stress relaxation resistance are shown.
  • Sn, Zn, Ag, Mn, B, P, Mg, Cr, Fe, Ti, Zr and Hf can be mentioned.
  • the total content is preferably 0.005 to 2.0 mass%, more preferably 0.01 to 1.5 mass%, and more preferably It is 0.03 to 0.8 mass%. If the total amount of these additive elements is too large, the conductivity is adversely affected. If the total amount of these additive elements is too small, the effect of adding these elements is hardly exhibited.
  • the stress relaxation resistance is improved.
  • the stress relaxation resistance is further improved by the synergetic effect when they are added together as compared to when each of them is added alone. In addition, it has the effect of significantly improving solder embrittlement.
  • the compound finely precipitates in a compound with Ni, Co, or Si, which is a main additive element, or a single substance, and contribute to precipitation hardening.
  • the compound precipitates in a size of 50 to 500 nm, and by suppressing grain growth, there is an effect of reducing the crystal grain size, and bending workability is improved.
  • a plate material (strip material) of precipitation type copper alloy is mentioned as an example and explained, it is possible to develop into a solid solution type alloy material, a dilute system alloy material, and a pure copper system material.
  • precipitation-type copper alloys were formed by homogenizing heat treatment and forming ingots in hot and cold steps, and subjected to final solution heat treatment in the temperature range of 700 to 1020 ° C. to resolute solute atoms. It is later manufactured to satisfy the required strength by aging precipitation heat treatment and finish cold rolling.
  • the conditions of aging precipitation heat treatment and finish cold rolling are adjusted according to the desired properties such as strength and conductivity.
  • the texture of the copper alloy is roughly determined by the recrystallization that occurs during the final solution heat treatment in this series of steps, and is ultimately determined by the rotation of the orientation that occurs during finish rolling.
  • a copper alloy material having a predetermined alloy component composition is melted in a high frequency melting furnace and cast to obtain an ingot [Step 1], the ingot Is subjected to homogenization heat treatment at 1020 to 700 ° C. for 10 minutes to 10 hours [Step 2], hot rolling at 2% or more at a working rate of 25% or more per pass in a temperature range of 1020 to (P + 30) ° C. [Step 3-1], cooling to a temperature of (P-30) ° C. or less by air cooling or water cooling [Step 3-2], 25% or less per pass in a temperature range of (P-30) to 400 ° C.
  • plate material of this invention by is mentioned.
  • the copper alloy sheet material of the present invention is preferably produced by the production method of the above embodiment, but in the crystal orientation analysis in EBSD measurement, if the above R satisfies the prescribed conditions, the above [Step 1] to [Step 12] is not necessarily bound by doing everything in this order.
  • [Step 10] may be completed as the final step.
  • one or more of the above [Step 10] to [Step 12] can be repeated twice or more. For example, cold rolling [process 11 '] of 2 to 45% may be performed before applying [process 10].
  • the end temperature of the hot rolling [Step 3-3] When the end temperature of the hot rolling [Step 3-3] is low, the deposition rate becomes slow, so the water cooling [Step 4] is not necessarily required.
  • Face milling [step 5] may be omitted depending on the scale of the material surface after hot rolling. In addition, the scale may be removed by dissolution by acid washing or the like.
  • hot rolling is performed at high temperature above dynamic recrystallization temperature
  • hot rolling at high temperature above room temperature and warm rolling below dynamic recrystallization temperature is sometimes different from the term warm rolling, including both It is common to assume. Also in the present invention, both are collectively called hot rolling.
  • the area ratio of Brass orientation, S orientation and Copper orientation is decreased and the area ratio of BR orientation, RDW orientation and Cube orientation is increased in the final solution heat treatment. It is preferable to select the conditions as described above in the hot working ([Step 3] consisting of [Step 3-1] to [Step 3-3]) performed after homogenization of the ingot.
  • hot working [Step 3] consisting of [Step 3-1] to [Step 3-3]
  • high temperature processing after homogenization is carried out at high temperature as much as possible for the purpose of reducing deformation resistance or in the case of precipitation type alloy for the purpose of suppressing a large amount of precipitation.
  • hot rolling ([step 3-1]) as the first hot rolling step, and thereafter cooling ([step 3-2]), and the second heat It is characterized in that rehot rolling ([step 3-3]) is performed at a temperature lower than the first step as an inter-rolling step.
  • the temperatures of the first step and the second step are defined as a specific temperature range defined using P ° C., which is a temperature at which solute atoms are completely dissolved.
  • the temperature of the first hot rolling step is 1020 to (P + 30) ° C.
  • this temperature is 1000 to (P + 50) ° C., more preferably 980 to (P + 70) ° C.
  • the temperature of the second hot rolling step is (P-30) to 400 ° C.
  • this temperature is too high, it becomes a structure equivalent to normal rolling, and conversely, when too low, the crack by intermediate temperature brittleness may occur.
  • it is (P-50) to 450 ° C., more preferably (P-70) to 500 ° C.
  • the temperature (T1) of the first hot rolling step is preferably higher than the temperature (T2) of the second hot rolling step (T1> T2), and as a typical example, the difference (T1-T2) is
  • the temperature is preferably 60 to 100 ° C., and more preferably 100 to 140 ° C.
  • the final temperature for cooling is (P-30) ° C. or less, and the lower limit thereof is practically not less than 450 ° C., although not particularly limited.
  • the significance of this cooling process is shown here.
  • the temperature zone between T1 and T2 defined using P ° C. is the temperature zone where deposition of the solute element is the fastest.
  • the solute element is solid-solved at a temperature higher than this intermediate temperature zone, the diffusion of atoms is slow at a temperature lower than this intermediate temperature zone, and the coarsening of the precipitates is slight.
  • the intermediate heat treatment performed after the hot rolling has an important meaning.
  • the intermediate heat treatment is preferably performed at a temperature of 600 to 900 ° C. during cold rolling as described above.
  • the intermediate heat treatment step a structure in which the entire surface is not recrystallized can be obtained. That is, among the crystal orientations in the rolled material, since there are crystal orientations with fast recovery and crystal orientations with a slow recovery, the structure becomes unevenly recrystallized due to the difference. This intentionally created inhomogeneity promotes preferential development of recrystallization texture in the intermediate recrystallization heat treatment [step 9].
  • the temperature P ° C. at which solute atoms are completely dissolved was determined by the following general method. After homogenizing the ingot at 1000 ° C for 1 hour, hot rolling and cold rolling are applied to form a plate, and then water annealing is performed after holding at 10 ° C for 30 seconds in a salt bath at 700 ° C to 1000 ° C for 30 seconds. To freeze the state of solid solution and precipitation at each temperature, and measure the conductivity. The conductivity was used as a substitute characteristic of the amount of the solid solution element, and the temperature at which the decrease in the conductivity with the increase of the heat treatment temperature was saturated was taken as the complete solution temperature P ° C. A typical conductivity change, and thereby the method of determining the temperature P (° C.), is schematically shown in FIG. As a typical example, it is practical that the temperature P is 750 to 950.degree.
  • the one-pass working ratio in the first hot rolling step is preferably 25% or more. If this is too low, destruction of the cast structure may not occur.
  • the upper limit is different depending on the specification of the rolling mill, and the upper limit is not particularly set, but is usually 50% or less.
  • the one-pass working ratio in the second hot rolling step is preferably 25% or less. If this is too high, processing cracks may occur due to processing at relatively low temperatures. Although the lower limit is not particularly set, it is usually 3% or more from the working efficiency.
  • the copper alloy sheet material of the present invention can satisfy, for example, the characteristics required for a copper alloy sheet material for a connector.
  • the minimum bending radius (r: mm) that allows bending without cracks in a 90 ° W bending test is specified as 0.2% proof stress, preferably 500 MPa or more (preferably 600 MPa or more, particularly preferably 700 MPa or more).
  • the value (r / t) divided by the plate thickness (t: mm) is 1 or less, and the conductivity is 30% IACS or more (preferably 35% IACS or more, particularly preferably 40% IACS or more).
  • the stress relaxation resistance (SR) of 30% or less (preferably 25% or less) can be satisfied by the measurement method of maintaining stress relaxation resistance at 150 ° C. described below for 1000 hours. can do.
  • Example 1 As shown in the composition of the column of alloy components in Table 1-1, 0.5 to 5.0 mass% in total of at least one of Ni and Co, and 0.1 to 1.5 mass% of Si in total An alloy containing the remainder, Cu and incidental impurities, was melted in a high-frequency melting furnace, and this was cast to obtain an ingot. Using this state as a providing material, test materials of copper alloy sheet materials of Invention Examples 1-1 to 1-19 and Comparative Examples 1-1 to 1-9 were manufactured in any of the following steps A to F. .
  • Step A Homogenizing heat treatment at 1020 to 700 ° C for 10 minutes to 10 hours, 3-pass hot rolling with a processing rate of 25% or more at a temperature range of 1020 to (P + 30) ° C, air cooling, (P-30) to 400 ° C 3-pass hot rolling, water cooling, 50 to 99% cold rolling, heat treatment holding at 600 to 900 ° C for 10 seconds to 5 minutes, with a working ratio of 25 to 55% in the temperature range Cold work, final solution heat treatment held at 750 to 1000 ° C. for 5 seconds to 1 hour. Thereafter, aging precipitation heat treatment is performed at 350 to 600 ° C. for 5 minutes to 20 hours, finish rolling at a working ratio of 2 to 45%, and temper annealing maintained at 300 to 700 ° C. for 10 seconds to 2 hours.
  • Step B Homogenizing heat treatment at 1020 to 700 ° C for 10 minutes to 10 hours, 3-pass hot rolling with a processing rate of 25% or more at a temperature range of 1020 to (P + 30) ° C, air cooling, (P-30) to 400 ° C 3-pass hot rolling, water cooling, 50 to 99% cold rolling, heat treatment holding at 600 to 900 ° C for 10 seconds to 5 minutes, with a working ratio of 25 to 55% in the temperature range Cold work, final solution heat treatment held at 750 to 1000 ° C. for 5 seconds to 1 hour. Then, rolling at 2 to 45% working ratio, aging precipitation heat treatment at 350 to 600 ° C for 5 minutes to 20 hours, finishing rolling at 2 to 45% working ratio, holding at 300 to 700 ° C for 10 seconds to 2 hours Perform temper annealing.
  • Step C Homogenizing heat treatment at 1020 to 700 ° C for 10 minutes to 10 hours, 3-pass hot rolling with a processing rate of 25% or more at a temperature range of 1020 to (P + 30) ° C, air cooling, (P-30) to 400 ° C 3-pass hot rolling, water cooling, 50 to 99% cold rolling, heat treatment holding at 600 to 900 ° C for 10 seconds to 5 minutes, with a working ratio of 25 to 55% in the temperature range Cold work, final solution heat treatment held at 750 to 1000 ° C. for 5 seconds to 1 hour. Thereafter, aging precipitation heat treatment is performed at 350 to 600 ° C. for 5 minutes to 20 hours.
  • Step D Homogenizing heat treatment at 1020 to 700 ° C for 10 minutes to 10 hours, 3-pass hot rolling with a processing rate of 25% or more at a temperature range of 1020 to (P + 30) ° C, air cooling, (P-30) to 400 ° C 3-pass hot rolling, water cooling, 50 to 99% cold rolling, heat treatment holding at 600 to 900 ° C for 10 seconds to 5 minutes, with a working ratio of 25 to 55% in the temperature range Cold work, final solution heat treatment held at 750 to 1000 ° C. for 5 seconds to 1 hour. Thereafter, rolling at a working ratio of 2 to 45% and aging precipitation heat treatment at 350 to 600 ° C. for 5 minutes to 20 hours are performed.
  • Step E Homogenizing heat treatment at 1020 to 700 ° C for 10 minutes to 10 hours, 3-pass hot rolling with a processing rate of 25% or more at a temperature range of 1020 to (P + 30) ° C, air cooling, (P-30) to 400 ° C
  • the final solution heat treatment is performed by 3-pass hot rolling, water cooling, 50 to 99% cold rolling, and holding at 750 to 1000 ° C. for 5 seconds to 1 hour at a processing rate of 25% or less in a temperature range.
  • aging precipitation heat treatment is performed at 350 to 600 ° C. for 5 minutes to 20 hours, finish rolling at a working ratio of 2 to 45%, and temper annealing maintained at 300 to 700 ° C. for 10 seconds to 2 hours.
  • Step F Homogenizing heat treatment at 1020 to 700 ° C. for 10 minutes to 10 hours, 3-pass hot rolling with a processing rate of 25% or more at a temperature range of 1020 to (P + 30) ° C., water cooling, 50 to 99% cold rolling, Heat treatment is performed at 600 to 900 ° C. for 10 seconds to 5 minutes, cold working at a working rate of 5 to 55%, and final solution heat treatment at 750 to 1000 ° C. for 5 seconds to 1 hour. Thereafter, aging precipitation heat treatment is performed at 350 to 600 ° C. for 5 minutes to 20 hours, finish rolling at a working ratio of 2 to 45%, and temper annealing maintained at 300 to 700 ° C. for 10 seconds to 2 hours.
  • FIG. 1 is an explanatory view of a test method for stress relaxation resistance, in which (a) shows a state before heat treatment and (b) shows a state after heat treatment.
  • FIG. 1A the position of the test piece 1 when an initial stress of 80% of the proof stress is applied to the test piece 1 held in a cantilever manner on the test stand 4 is a distance of ⁇ 0 from the reference is there. This is held in a thermostat at 150 ° C. for 1000 hours (heat treatment in the state of the test piece 1), and the position of the test piece 2 after removing the load is H t from the reference as shown in FIG. Distance. 3 is a test piece when no stress is applied, and its position is the distance of H 1 from the reference.
  • the stress relaxation rate (%) was calculated as (H t -H 1 ) / ( ⁇ 0 -H 1 ) ⁇ 100.
  • ⁇ 0 is the distance from the reference to the test specimen 1
  • H 1 is the distance from the reference to the test specimen 3
  • H t is the distance from the reference to the test specimen 2.
  • inventive examples 1-1 to 1-19 were excellent in bending workability, proof stress, conductivity, and stress relaxation resistance.
  • Table 1-2 when the conditions of the present invention were not satisfied, the characteristics were inferior. That is, in Comparative Example 1-1, since the total amount of Ni and Co was small, the density of the compound (precipitate) contributing to the precipitation hardening was lowered and the strength was inferior. In addition, Si which does not form a compound with Ni or Co excessively dissolves in the metal structure and the conductivity is inferior. In Comparative Example 1-2, the conductivity was inferior because the total amount of Ni and Co was large. Comparative Example 1-3 was inferior in strength due to the small amount of Si. In Comparative Example 1-4, the conductivity was inferior because of the large amount of Si. Comparative Examples 1-5 to 1-9 had low R and inferior bending workability.
  • Example 2 Invention Examples 2-1 to 2-17 and Comparative Examples 2-1 to 2 in the same manner as in Example 1 with respect to a copper alloy having the composition shown in the column of alloy components in Table 2 and the balance being Cu and incidental impurities
  • a sample of a copper alloy sheet material of -3 was produced, and the characteristics were examined in the same manner as in Example 1. The results are shown in Table 2.
  • Inventive Example 2-1 to Inventive Example 2-17 were excellent in bending workability, proof stress, conductivity, and stress relaxation resistance. On the other hand, when the requirements of the present invention were not satisfied, the characteristics were inferior. That is, Comparative Examples 2-1, 2-2, and 2-3 (all, the comparative examples of the invention according to the item (3)) have a large amount of addition of elements other than Ni, Co and Si. , Conductivity was poor.
  • Example 3 With respect to a copper alloy having the composition shown in Table 3 and the balance being Cu and incidental impurities, the ingot is subjected to homogenization heat treatment at 1020 to 700 ° C. for 10 minutes to 10 hours, then water cooling after hot rolling shown in Table 4 Face milling, 50 to 99% cold rolling, heat treatment held at 600 to 900 ° C for 10 seconds to 5 minutes, cold working at 5 to 55% working ratio, held at 750 to 1000 ° C for 5 seconds to 1 hour Perform final solution heat treatment. After that, aging precipitation heat treatment for 5 minutes to 20 hours at 350 to 600 ° C, finish rolling at a working ratio of 2 to 45%, temper annealing for holding for 10 seconds to 2 hours at 300 to 700 ° C, Manufactured. The characteristics were investigated in the same manner as in Example 1. The results are shown in Table 4.
  • Inventive Example 3-1 to Inventive Example 3-4 were excellent in bending workability, proof stress, conductivity, and stress relaxation resistance. On the other hand, when the requirements of the present invention were not satisfied, the characteristics were inferior. That is, in Comparative Examples 3-1 to 3-4, since the condition of the hot working deviates from the condition defined in the present invention, R specified in the present invention does not satisfy the predetermined value, and the bendability is inferior.
  • an on-vehicle component such as a connector material or a material of an electric / electronic device (in particular, a base material thereof).
  • Comparative Example 101 Condition of JP 2009-007666 A metal element similar to that of the invention example 1-1 was blended, and an alloy composed of Cu and incidental impurities with the balance was melted in a high frequency melting furnace, This was cast at a cooling rate of 0.1 to 100 ° C./sec to obtain an ingot. After holding this at 900 ° C. to 1020 ° C. for 3 minutes to 10 hours, it was hot-worked and then water-quenched to carry out facing for oxide scale removal. In the subsequent steps, a copper alloy c01 was produced by performing the treatments of steps A-3 and B-3 described below.
  • the manufacturing process includes one or more solution heat treatment, in which the steps are classified before and after the last solution heat treatment, and the steps up to intermediate solution treatment are designated as A-3, It was designated as B-3 step in the step after intermediate solution treatment.
  • the working ratio and the number of passes of hot working the conditions of 800 to 1020 ° C., the one-pass working ratio of 35 to 40%, and the number of passes 2 to 5 which were common at the time of filing the present application were adopted.
  • Step A-3 Cold work with a reduction in area of 20% or more, heat treatment for 5 minutes to 10 hours at 350 to 750 ° C., cold work with a reduction in area of 5 to 50%, 800 A solution heat treatment is performed at about 1000 ° C. for 5 seconds to 30 minutes.
  • Step B-3 Cold work with a reduction in area of 50% or less, heat treatment at 400 to 700 ° C. for 5 minutes to 10 hours, cold work with a reduction in area of 30% or less, Apply temper annealing at 550 ° C. for 5 seconds to 10 hours.
  • the obtained test body c01 is different from the above example in the presence or absence of the second hot rolling step in the present application of the hot rolling condition with respect to manufacturing conditions, and does not satisfy the required characteristics for bending workability because R is low. It became a result.
  • test body c02 is the same as the above-described example in the presence or absence of the heat treatment [step 7] and the cold working [step 8] in the present application and the presence or absence of the second hot rolling step in the present application of the hot rolling conditions. It differs in point, and it became the result which does not satisfy bending workability because R is low.
  • Comparative Example 103 Condition of JP-A-2008-223136 The copper alloy shown in Example 1 was melted and cast using a vertical continuous casting machine. A sample of 50 mm in thickness was cut out from the obtained slab (180 mm in thickness), heated to 950 ° C., extracted, and hot rolling was started. At this time, a pass schedule was set so that the rolling reduction in a temperature range of 950 to 700 ° C. would be 60% or more and rolling could be performed in a temperature range of less than 700 ° C. The final pass temperature for hot rolling is between 600 and 400 ° C. The total hot-rolling rate from the slab is about 90%. After hot rolling, the surface oxide layer was removed by mechanical polishing (face grinding).
  • the aging treatment temperature was set to 450 ° C., and the aging time was adjusted to a time at which the hardness peaked at 450 ° C. aging depending on the alloy composition.
  • the optimum solution treatment conditions and aging treatment time are grasped by preliminary experiments according to such alloy composition.
  • finish cold rolling was performed at a rolling ratio.
  • the final cold-rolled product was further subjected to low-temperature annealing for 5 minutes in a 400 ° C. furnace.
  • a test material c03 was obtained.
  • it was chamfered on the way as needed, and the plate thickness of the test material was equalized to 0.2 mm.
  • the main production conditions are described below.
  • the obtained test body c03 is the same as the above-described Example 1 under the production conditions, the presence or absence of the cooling step of the first step and the second step in the hot rolling in the present application, the working ratio of the second step, and the heat treatment in the present application [
  • the difference between the step 7] and the presence or absence of cold working [step 8] is that the bending workability is not satisfied because R is low.
  • Comparative Example 104 Condition of Comparative Example of Japanese Patent Application Laid-Open No. 2008-223136
  • a test material c04 is obtained in the same manner as in Comparative Example 103 except that the processing conditions of the following items are changed as follows.
  • the obtained test body c04 is the same as Example 1 described above in the presence or absence of the cooling step of the first step and the second step in the hot rolling in the present application.
  • the difference in the presence or absence of the heat treatment [step 7] and the cold working [step 8] in the present application resulted in not satisfying the bending workability because R is low.

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Abstract

L'invention porte sur une feuille d'alliage de cuivre qui présente d'excellentes caractéristiques en termes d'aptitude à la flexion et de résistance et qui est appropriée pour être utilisée dans des grilles de connexion, des connecteurs et des matériaux de bornes pour des appareils électriques/électroniques, des connecteurs ou des matériaux de bornes pour le montage dans des véhicules, des relais, des commutateurs et autres. L'invention porte également sur un procédé de fabrication de la feuille d'alliage de cuivre. La feuille d'alliage de cuivre, une fois analysée pour l'orientation des cristaux par EBSD (diffraction des électrons à rétrodiffusion), présente une valeur de R définie par l'équation de 1 ou plus : R=([BR]+[RDW]+[W])/([C]+[S]+[B]), où [BR], [RDW], [W], [C], [S], et [B] sont respectivement les proportions de superficie des composants de texture ayant respectivement des orientations BR {362}<853>, une orientation cubique à rotation RD {012}<100>, une orientation cubique {100}<001>, une orientation du cuivre {121}<111>, une orientation S {231}<346>, et une orientation du laiton {110}<112>. La feuille présente une résistance à la charge d'épreuve de 500 MPa ou plus et une conductivité de 30 % IACS ou plus.
PCT/JP2010/071518 2009-12-02 2010-12-01 Feuille d'alliage de cuivre et son procédé de fabrication WO2011068135A1 (fr)

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JP2011513178A JP4885332B2 (ja) 2009-12-02 2010-12-01 銅合金板材およびその製造方法
KR1020127012528A KR101419147B1 (ko) 2009-12-02 2010-12-01 구리합금 판재 및 그 제조방법
EP10834585.1A EP2508635B1 (fr) 2009-12-02 2010-12-01 Feuille d'alliage de cuivre et son procédé de fabrication
CN201080051567.1A CN102695811B (zh) 2009-12-02 2010-12-01 铜合金板材及其制造方法
US13/486,903 US20120267013A1 (en) 2009-12-02 2012-06-01 Copper alloy sheet material and method of producing the same

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US10153063B2 (en) 2011-11-07 2018-12-11 Mitsubishi Materials Corporation Copper alloy for electronic devices, method of manufacturing copper alloy for electronic devices, copper alloy plastic working material for electronic devices, and component for electronic devices
US10458003B2 (en) * 2011-11-14 2019-10-29 Mitsubishi Materials Corporation Copper alloy and copper alloy forming material
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JP2018162489A (ja) * 2017-03-24 2018-10-18 Ｊｘ金属株式会社 電子材料用銅合金
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KR20120104544A (ko) 2012-09-21
EP2508635B1 (fr) 2017-08-23
JPWO2011068135A1 (ja) 2013-04-18
CN102695811B (zh) 2014-04-02
EP2508635A1 (fr) 2012-10-10
CN102695811A (zh) 2012-09-26
KR101419147B1 (ko) 2014-07-11
JP4885332B2 (ja) 2012-02-29
US20120267013A1 (en) 2012-10-25

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