WO2011068135A1 - Copper alloy sheet and process for producing same - Google Patents

Copper alloy sheet and process for producing same Download PDF

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Publication number
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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French (fr)
Japanese (ja)
Inventor
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/en
Priority to EP10834585.1A priority patent/EP2508635B1/en
Priority to CN201080051567.1A priority patent/CN102695811B/en
Priority to KR1020127012528A priority patent/KR101419147B1/en
Publication of WO2011068135A1 publication Critical patent/WO2011068135A1/en
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

Provided is a copper alloy sheet which has excellent bendability and excellent strength and is suitable for use in lead frames, connectors, and terminal materials for electric/electronic appliances, connectors or terminal materials for vehicular mounting, relays, switches, and the like. Also provided is a process for producing the copper alloy sheet. The copper alloy sheet, when analyzed for crystal orientation by EBSD (electron back scatter diffraction), has a value of R defined by the equation of 1 or greater: R=([BR]+[RDW]+[W])/([C]+[S]+[B]) where [BR], [RDW], [W], [C], [S], and [B] respectively are the areal proportions of texture components respectively having BR orientation {362}<853>, RD-rotated-cube orientation {012}<100>, cube orientation {100}<001>, copper orientation {121}<111>, S orientation {231}<346>, and brass orientation {110}<112>. The sheet has a proof strength of 500 MPa or greater and a conductivity of 30% IACS or higher.

Description

銅合金板材およびその製造方法Copper alloy sheet and method of manufacturing the same
　本発明は銅合金板材およびその製造方法に関し、詳しくは車載部品用や電気・電子機器用のリードフレーム、コネクタ、端子材、リレー、スイッチ、ソケットなどに適用される銅合金板材およびその製造方法に関する。 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 .
　車載部品用や電気・電子機器用のリードフレーム、コネクタ、端子材、リレー、スイッチ、ソケットなどの用途に使用される銅合金板材に要求される特性項目としては、例えば、導電率、耐力（降伏応力）、引張強度、曲げ加工性、耐応力緩和特性などがある。近年、電気・電子機器の小型化、軽量化、高機能化、高密度実装化や、使用環境の高温化に伴って、これらの要求特性のレベルが高まっている。
　このため、近年の銅合金板材が使用される状況には、以下のような変化が挙げられる。一つ目に、自動車や電機・電子機器の高機能化とともに、コネクタの多極化が進行しているため、端子や接点部品の一つ一つの小型化が進行している。例えば、タブ幅が約１．０ｍｍの端子を０．６４ｍｍへダウンサイズする動きが進んでいる。
　二つ目に、鉱物資源の低減や、部品の軽量化を背景に、基体材料の薄肉化が進行しており、なおかつバネ接圧を保つために、従来よりも高強度な基体材料が使用されている。
　三つ目に使用環境の高温化が進行している。例えば自動車部品では、二酸化炭素発生量の低減のために、車体軽量化が進められている。このため、従来、ドアに設置していたようなエンジン制御用のＥＣＵなどの電子機器をエンジンルーム内やエンジン付近に設置し、電子機器とエンジンの間のワイヤーハーネスを短くする動きが進んでいる。 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. In recent years, with the miniaturization, weight reduction, high functionality, high density mounting, and high temperature of the use environment of electric / electronic equipment, 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. First, with the advancement of functions of automobiles, electrical and electronic devices, and the multipolarity of connectors, the miniaturization of terminals and contact parts is progressing. For example, there is an ongoing movement to downsize terminals having a tab width of about 1.0 mm to 0.64 mm.
Second, with the background of reduction of mineral resources and weight reduction of parts, thinning of base material is progressing, and base material of higher strength is used to maintain spring contact pressure. ing.
Thirdly, the temperature of the usage environment is increasing. For example, in the case of automobile parts, weight reduction of the vehicle body has been promoted in order to reduce the amount of carbon dioxide generated. For this reason, there is an increasing movement to shorten the wire harness between the electronic device and the engine by installing electronic devices such as an ECU for engine control, which has conventionally been installed at a door, in the engine room or near the engine. .
　そして、上記の変化に伴い、銅合金板材には下記のような問題が生じている。
　第一に、端子の小型化に伴い、接点部分やバネ部分に施される曲げ加工の曲げ半径は小さくなり、材料には従来よりも厳しい曲げ加工が施される。そのため、材料にクラックが発生する問題が生じている。
　第二に、材料の高強度化に伴い、材料にクラックが発生する問題が生じている。これは、材料の曲げ加工性が、一般的に強度とトレードオフの関係にあるためである。
　第三に、接点部分やバネ部分に施される曲げ加工部にクラックが発生すると、接点部分の接圧が低下することにより、接点部分の接触抵抗が上昇し、電気的接続が絶縁され、コネクタとしての機能が失われるため、重大な問題となる。 And with the above-mentioned change, the following problems have arisen to a copper alloy board material.
First, with the miniaturization of terminals, the bending radius of the bending applied to the contact portion and the spring portion becomes smaller, and the material is subjected to bending that is more severe than before. Therefore, the problem that a crack generate | occur | produces in the material has arisen.
Second, with the increase in strength of materials, there is a problem that cracks occur in the materials. This is because the bending processability of the material generally has a trade-off relationship with the strength.
Thirdly, if a crack is generated in the bent portion applied to the contact portion or the spring portion, the contact pressure of the contact portion is reduced, the contact resistance of the contact portion is increased, and the electrical connection is insulated, and the connector As the function is lost, it becomes a serious problem.
　この曲げ加工性向上の要求に対して、結晶方位の制御によって解決する提案がいくつかなされている。特許文献１では、Ｃｕ－Ｎｉ－Ｓｉ系銅合金において、結晶粒径と、｛３１１｝、｛２２０｝、｛２００｝面からのＸ線回折強度がある条件を満たすような結晶方位の場合に、曲げ加工性が優れることが見出されている。また、特許文献２では、Ｃｕ－Ｎｉ－Ｓｉ系銅合金において、｛２００｝面および｛２２０｝面からのＸ線回折強度がある条件を満足する結晶方位の場合に、曲げ加工性が優れることが見出されている。また、特許文献３では、Ｃｕ－Ｎｉ－Ｓｉ系銅合金において、Ｃｕｂｅ方位｛１００｝＜００１＞の割合の制御によって曲げ加工性が優れることが見出されている。その他、特許文献４～８においても、種々の原子面についてのＸ線回折強度で規定された曲げ加工性に優れる材料が提案されている。特許文献４では、Ｃｕ－Ｎｉ－Ｃｏ－Ｓｉ系銅合金において、｛２００｝面からのＸ線回折強度が、｛１１１｝面、｛２００｝面、｛２２０｝面及び｛３１１｝面からのＸ線回折強度に対してある条件を満足する結晶方位の場合に、曲げ加工性が優れることが見出されている。特許文献５では、Ｃｕ－Ｎｉ－Ｓｉ系銅合金において、｛４２０｝面および｛２２０｝面からのＸ線回折強度がある条件を満足する結晶方位の場合に、曲げ加工性が優れることが見出されている。特許文献６では、Ｃｕ－Ｎｉ－Ｓｉ系銅合金において、｛１２３｝＜４１２＞方位に関してある条件を満足する結晶方位の場合に、曲げ加工性が優れることが見出されている。特許文献７では、Ｃｕ－Ｎｉ－Ｓｉ系銅合金において、｛１１１｝面、｛３１１｝面及び｛２２０｝面からのＸ線回折強度がある条件を満足する結晶方位の場合に、Ｂａｄ　Ｗａｙ（後述）の曲げ加工性が優れることが見出されている。また、特許文献８では、Ｃｕ－Ｎｉ－Ｓｉ系銅合金において、｛２００｝面、｛３１１｝面及び｛２２０｝面からのＸ線回折強度がある条件を満足する結晶方位の場合に、曲げ加工性が優れることが見出されている。
　特許文献１、２、４、５、７、８におけるＸ線回折強度による規定は、板面方向（圧延法線方向、ＮＤ）への特定の結晶面の集積について規定したものである。 Several proposals have been made to solve this demand for improved bending workability by controlling the crystal orientation. In 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. Further, in 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>. In addition, Patent Documents 4 to 8 also propose materials excellent in bending workability defined by X-ray diffraction intensities of various atomic planes. In Patent Document 4, in the Cu-Ni-Co-Si copper alloy, 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. In 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. In 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. In 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).
特開２００６－００９１３７号公報JP, 2006-009137, A 特開２００８－０１３８３６号公報JP, 2008-013836, A 特開２００６－２８３０５９号公報JP 2006-283059 A 特開２００９－００７６６６号公報JP, 2009-007666, A 特開２００８－２２３１３６号公報JP 2008-223136 A 特開２００７－０９２１３５号公報JP 2007-092135 A 特開２００６－０１６６２９号公報JP, 2006-016629, A 特開平１１－３３５７５６号公報Japanese Patent Application Laid-Open No. 11-335756
　ところで、特許文献１または特許文献２に記載された発明は、特定の結晶面からのＸ線回折による結晶方位の測定に基づくものであって、ある広がりを持った結晶方位の分布の中のごく一部の特定の面にのみ関するものである。しかも、板面方向（ＮＤ）の結晶面のみを測定しているに過ぎず、圧延方向（ＲＤ）や板幅方向（ＴＤ）にどの結晶面が向いているかについては制御できない。よって、曲げ加工性を完全に制御するには、なお不十分な方法であった。また、特許文献３に記載された発明においては、Ｃｕｂｅ方位の有効性が指摘されているが、その他の結晶方位成分については制御されておらず、曲げ加工性の改善が不十分な場合があった。また、特許文献４～８では、それぞれ上記特定の結晶面または方位について測定、制御する検討しかなされておらず、特許文献１～３と同様に、曲げ加工性の改善が不十分な場合があった。 By the way, the invention described in 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
　上記のような課題に鑑み、本発明の目的は、曲げ加工性に優れ、優れた強度を有し、電気・電子機器用のリードフレーム、コネクタ、端子材等、自動車車載用などのコネクタや端子材、リレー、スイッチなどに適した銅合金板材およびその製造方法を提供することにある。 In view of the above problems, it is an object of the present invention to have excellent bending processability and excellent strength, and lead frames, connectors, terminal materials for electric and electronic devices, connectors and terminals for automotive vehicles, etc. It is an object of the present invention to provide a copper alloy sheet material suitable for materials, relays, switches and the like and a method of manufacturing the same.
　本発明者らは、種々検討を重ね、電気・電子部品用途に適した銅合金について研究を行い、ＥＢＳＤ法によって特徴付けられる、ＢＲ方位、ＲＤ－Ｒｏｔａｔｅｄ－Ｃｕｂｅ方位（以下、ＲＤＷ方位ともいう）及びＣｕｂｅ方位を増加させ、なおかつ、Ｃｏｐｐｅｒ方位、Ｓ方位、Ｂｒａｓｓ方位を低減することにより、曲げ加工時のクラックが抑制されることを見出し、さらに、それらの各方位の集合組織方位成分の面積率を所定の比率とすることで曲げ加工性を著しく良化できることを見出した。また、それに加えて、本合金系において特定の添加元素を用いることにより、導電率や曲げ加工性を損なうことなく、強度や耐応力緩和特性を向上させうることを見出した。本発明は、これらの知見に基づきなされるに至ったものである。 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.
　すなわち、本発明は、以下の解決手段を提供する。
（１）ＥＢＳＤ（Ｅｌｅｃｔｒｏｎ　Ｂａｃｋ　Ｓｃａｔｔｅｒ　Ｄｉｆｆｒａｃｔｉｏｎ：電子後方散乱回折）測定における結晶方位解析において、ＢＲ方位｛３　６　２｝＜８　５　３＞、ＲＤ－Ｒｏｔａｔｅｄ－Ｃｕｂｅ方位｛０　１　２｝＜１　０　０＞、Ｃｕｂｅ方位｛１　０　０｝＜０　０　１＞、Ｃｏｐｐｅｒ方位｛１　２　１｝＜１　１　１＞、Ｓ方位｛２　３　１｝＜３　４　６＞、Ｂｒａｓｓ方位｛１　１　０｝＜１　１　２＞のそれぞれの集合組織方位成分の面積率を［ＢＲ］、［ＲＤＷ］、［Ｗ］、［Ｃ］、［Ｓ］、［Ｂ］とした時に、
Ｒ＝（［ＢＲ］＋［ＲＤＷ］＋［Ｗ］）／（［Ｃ］＋［Ｓ］＋［Ｂ］）
と定義されるＲが１以上であり、耐力が５００ＭＰａ以上、導電率が３０％ＩＡＣＳ以上であることを特徴とする銅合金板材。
（２）ＮｉとＣｏのいずれか１種または２種を合計で０．５～５．０ｍａｓｓ％、Ｓｉを０．１～１．５ｍａｓｓ％含有し、残部が銅及び不可避不純物からなる合金組成を有することを特徴とする（１）に記載の銅合金板材。
（３）さらに、Ｓｎ、Ｚｎ、Ａｇ、Ｍｎ、Ｂ、Ｐ、Ｍｇ、Ｃｒ、Ｆｅ、Ｔｉ、ＺｒおよびＨｆからなる群から選ばれる少なくとも１種を合計で０．００５～２．０ｍａｓｓ％含有することを特徴とする（２）に記載の銅合金板材。
（４）コネクタ用材料であることを特徴とする（１）～（３）のいずれか１項に記載の銅合金板材。
（５）（１）～（４）の銅合金板材からなるコネクタ。
（６）（１）～（５）のいずれか１項に記載の銅合金板材を製造する方法であって、前記銅合金を与える合金組成の銅合金に、鋳造［工程１］、均質化熱処理［工程２］、熱間加工［工程３］、冷間圧延［工程６］、熱処理［工程７］、冷間圧延［工程８］、最終溶体化熱処理［工程９］をこの順に施し、その後に、時効析出熱処理［工程１０］を施し、上記熱間加工［工程３］は、溶質原子の完全固溶温度をＰ℃とした場合に、まず１０２０℃以下で（Ｐ＋３０）℃以上の温度において１パス加工率が２５％以上の熱間圧延を２パス以上行った後に、（Ｐ－３０）℃以下まで冷却し、（Ｐ－３０）℃以下で４００℃以上の温度において、１パス加工率が２５％以下の熱間圧延を２パス以上行うことからなることを特徴とする銅合金板材の製造方法。
（７）前記時効析出熱処理［工程１０］の後に、冷間圧延［工程１１］、及び調質焼鈍［工程１２］をこの順に施すことを特徴とする（６）項に記載の銅合金板材の製造方法。 That is, the present invention provides the following solutions.
(1) 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 When the area ratio of each texture orientation component of 12> is set as [BR], [RDW], [W], [C], [S], [B],
R = ([BR] + [RDW] + [W]) / ([C] + [S] + [B])
A copper alloy sheet material characterized in that R is defined as 1 or more, the proof stress is 500 MPa or more, and the conductivity is 30% IACS or more.
(2) an alloy composition containing 0.5 to 5.0 mass% in total of one or two or more of Ni and Co, 0.1 to 1.5 mass% of Si, and the balance being copper and unavoidable impurities It has, The copper alloy board material as described in (1) characterized by having.
(3) Furthermore, a total of 0.005 to 2.0 mass% of at least one selected from the group consisting of Sn, Zn, Ag, Mn, B, P, Mg, Cr, Fe, Ti, Zr and Hf is contained in total The copper alloy sheet material according to (2), characterized in that
(4) The copper alloy sheet material according to any one of (1) to (3), which is a material for a connector.
(5) A connector comprising the copper alloy sheet material of (1) to (4).
(6) A method for producing the copper alloy sheet material according to any one of (1) to (5), wherein the copper alloy having an alloy composition giving the copper alloy is subjected to casting [step 1], homogenization heat treatment [Step 2], hot working [Step 3], cold rolling [Step 6], heat treatment [Step 7], cold rolling [Step 8], final solution heat treatment [Step 9] in this order, and then Aging precipitation heat treatment [Step 10] is performed, and the above-mentioned hot working [Step 3] is performed first at 1020 ° C. or less and (P + 30) ° C. or more at 1 ° C. or less, where P ° C. is the solid solution temperature of solute atoms. 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.
　本発明の銅合金板材は、曲げ加工性に優れ、優れた強度を有し、電気・電子機器用のリードフレーム、コネクタ、端子材等、自動車車載用などのコネクタや端子材、リレー、スイッチなどに好適である。
　また、本発明の銅合金板材の製造方法は、上記の曲げ加工性に優れ、優れた強度を有し、電気・電子機器用のリードフレーム、コネクタ、端子材等、自動車車載用などのコネクタや端子材、リレー、スイッチなどに好適な銅合金板材を製造する方法として好適なものである。 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.
耐応力緩和特性の試験方法の説明図であり、（ａ）は熱処理前、（ｂ）は熱処理後の状態をそれぞれ示す。It is explanatory drawing of the test method of a stress relaxation characteristic, (a) is before heat processing, (b) shows the state after heat processing, respectively. 熱処理温度の上昇にともなう導電率変化の典型例を示すグラフであり、それにより溶質原子が完全に固溶する温度（Ｐ）℃を決定する方法を模式的に示すものである。It is a graph which shows the typical example of the electric conductivity change accompanying the raise of heat processing temperature, and shows typically the method of determining temperature (P) (degree) C in which a solute atom completely dissolves.
　本発明の銅合金板材の好ましい実施の態様について、詳細に説明する。ここで、「銅合金材料」とは、銅合金素材が所定の形状（例えば、板、条、箔、棒、線など）に加工されたものを意味する。そのなかで板材とは、特定の厚みを有し形状的に安定しており面方向に広がりをもつものを指し、広義には条材を含む意味である。ここで、板材において、「材料表層」とは、「板表層」を意味し、「材料の深さ位置」とは、「板厚方向の位置」を意味する。板材の厚さは特に限定されないが、本発明の効果が一層よく顕れ実際的なアプリケーションに適合することを考慮すると、８～８００μｍが好ましく、５０～７０μｍがより好ましい。
　なお、本発明の銅合金板材は、その特性を圧延板の所定の方向における原子面の集積率で規定するものであるが、これは銅合金板材としてそのような特性を有していれば良いのであって、銅合金板材の形状は板材や条材に限定されるものではなく、本発明では、管材も板材として解釈して取り扱うことができるものとする。 A preferred embodiment of the copper alloy sheet of the present invention will be described in detail. Here, "copper alloy material" means one obtained by processing a copper alloy material into a predetermined shape (e.g., plate, strip, foil, bar, wire, etc.). Among them, 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. Here, in the plate material, “material surface layer” means “plate surface layer”, and “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 μm, more preferably 50 to 70 μm, in consideration of the fact that the effects of the present invention are more apparent and suitable for practical applications.
In addition, although 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.
　銅合金板材の曲げ加工時のクラックが発生する原因を明らかにするために、本発明者らは、曲げ変形した後の材料の金属組織を詳細に調査した。その結果、基体材料は均一に変形しているのではなく、特定の結晶方位の領域のみに変形が集中し、不均一な変形が進行することが観察された。そして、その不均一変形により、曲げ加工した後の基体材料表面には、数ミクロンの深さのシワや、微細なクラックが発生することが解った。
　そして、ＢＲ方位とＲＤＷ方位とＣｕｂｅ方位が多く、Ｃｏｐｐｅｒ方位とＳ方位とＢｒａｓｓ方位が少ない場合に、不均一な変形が抑制され、基体材料の表面に発生するシワが低減され、クラックが抑制されることが解った。
　曲げ加工した断面部の組織観察において、ＢＲ方位とＲＤＷ方位とＣｕｂｅ方位の結晶粒内には局所変形帯が少なく、Ｃｏｐｐｅｒ方位とＳ方位とＢｒａｓｓ方位の結晶粒内には、局所変形帯が多く見られることも確認された。 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.
When the BR orientation, the RDW orientation, and the Cube orientation are many and the Copper orientation, the S orientation, and the Brass orientation are small, non-uniform deformation is suppressed, wrinkles generated on the surface of the base material are reduced, and cracks are suppressed. It turned out that
There are few local deformation bands in crystal grains of BR orientation, RDW orientation and Cube orientation, and there are many local deformation bands in crystal grains of Copper orientation, S orientation and Brass orientation in the texture observation of the cross-sectional part that has been bent. It was also confirmed that it could be seen.
（ＥＢＳＤ測定による規定）
　ＥＢＳＤ法で規定される、ＢＲ方位｛３　６　２｝＜８　５　３＞、ＲＤ－Ｒｏｔａｔｅｄ－Ｃｕｂｅ方位｛０　１　２｝＜１　０　０＞、Ｃｕｂｅ方位｛１　０　０｝＜０　０　１＞、Ｃｏｐｐｅｒ方位｛１　２　１｝＜１　１　１＞、Ｓ方位｛２　３　１｝＜３　４　６＞、Ｂｒａｓｓ方位｛１　１　０｝＜１　１　２＞のそれぞれの集合組織方位成分の面積率を［ＢＲ］、［ＲＤＷ］、［Ｗ］、［Ｃ］、［Ｓ］、［Ｂ］とした時に、Ｒ＝（［ＢＲ］＋［ＲＤＷ］＋［Ｗ］）／（［Ｃ］＋［Ｓ］＋［Ｂ］）と定義されるＲが１以上のときに、上記の効果が得られる。好ましくは１．１以上、更に好ましくは１．２以上６以下である。従来、これらの方位を有する原子面の面積率を同時に制御したものは知られていない。 (Specified by EBSD measurement)
BR orientation {3 6 2} <8 5 3>, RD-Rotated-Cube orientation {0 1 2} <1 0 0>, Cube orientation {1 0 0} <0 0 1> specified by EBSD method The area ratio of each texture orientation component of Copper orientation {1 2 1} <1 1 1>, S orientation {2 3 1} <3 4 6>, Brass orientation {1 1 0} <1 1 2> R = ([BR] + [RDW] + [W]) / ([C] + [S] where BR], [RDW], [W], [C], [S], and [B]. The above effect is obtained when R defined as + [B] is 1 or more. Preferably they are 1.1 or more, More preferably, they are 1.2 or more and 6 or less. Conventionally, there is not known one in which the area ratio of atomic planes having these orientations is simultaneously controlled.
　本明細書における結晶方位の表示方法は、材料の圧延方向（ＲＤ）をＸ軸、板幅方向（ＴＤ）をＹ軸、圧延法線方向（ＮＤ）をＺ軸の直角座標系を取り、材料中の各領域がＺ軸に垂直な（圧延面に平行な）結晶面の指数（ｈｋｌ）と、Ｘ軸に平行な結晶方向の指数[ｕｖｗ]とを用いて、（ｈｋｌ）[ｕｖｗ]の形で示す。また、（１　３　２）[６　－４　３]と（２　３　１）[３　－４　６]などのように、銅合金の立方晶の対称性のもとで等価な方位については、ファミリーを表すカッコ記号を使用し、{ｈｋｌ}＜ｕｖｗ＞と示す。本発明における６種類の方位は、上記のような指数でそれぞれ示される。 In the crystal orientation display method in this specification, 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. Also, for equivalent orientations under the cubic symmetry of copper alloys, such as (1 32) [6-4 3] and (2 3 1) [3-4 6] etc. Use the parenthesis symbol to indicate, {hkl} <uvw>. The six types of orientations in the present invention are indicated by the indices as described above.
　本発明における上記結晶方位の解析には、ＥＢＳＤ法を用いた。ＥＢＳＤとは、Ｅｌｅｃｔｒｏｎ　Ｂａｃｋ　Ｓｃａｔｔｅｒ　Ｄｉｆｆｒａｃｔｉｏｎ（電子後方散乱回折）の略で、走査電子顕微鏡（Ｓｃａｎｎｉｎｇ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｐｅ：ＳＥＭ）内で試料に電子線を照射したときに生じる反射電子菊池線回折（菊池パターン）を利用した結晶方位解析技術のことである。本発明においては、結晶粒を２００個以上含む、５００μｍ四方の試料面積に対し、０．５μｍのステップでスキャンし、方位を解析した。
　本発明においては、前記ＢＲ、ＲＤ－Ｒｏｔａｔｅｄ－Ｃｕｂｅ（ＲＤＷ）、Ｃｕｂｅ（Ｗ）、Ｃｏｐｐｅｒ（Ｃ）、ＳおよびＢｒａｓｓ（Ｂ）の方位の各集合組織方位成分をもつ結晶粒とその原子面の面積を、以下に述べる所定のずれ角度の範囲内にあるかどうかで規定する。
　上記指数で示される理想方位からのずれ角度については、（ｉ）各測定点の結晶方位と、（ｉｉ）対象となる理想方位としてのＢＲ、ＲＤＷ、Ｃｕｂｅ、Ｃｏｐｐｅｒ、Ｓ、Ｂｒａｓｓのいずれかの方位とについて、（ｉ）と（ｉｉ）に共通の回転軸を中心に回転角を計算し、そのずれ角度とした。例えば、Ｓ方位（２　３　１）[６　－４　３]に対して、（１　２　１）[１　－１　１]は（２０　１０　１７）方向を回転軸にして、１９．４°回転した関係になっており、この角度をずれ角度とした。前記共通の回転軸は４０以下の３つの整数であるが、その内で最も小さいずれ角度で表現できるものを採用した。全ての測定点に対してこのずれ角度を計算して小数第一位までを有効数字とし、ＢＲ方位、ＲＤＷ方位、Ｃｕｂｅ方位、Ｃｏｐｐｅｒ方位、Ｓ方位、Ｂｒａｓｓ方位のそれぞれ前記ずれ角から１０°以下の方位を持つ結晶粒の面積を全測定面積で除し、それぞれの方位の原子面の面積率とした。
　ＥＢＳＤによる方位解析において得られる情報は、電子線が試料に侵入する数１０ｎｍの深さまでの方位情報を含んでいるが、測定している広さに対して充分に小さいため、本明細書中では面積率として記載した。
　結晶方位の解析にＥＢＳＤ測定を用いることにより、従来のＸ線回折法による板面方向（ＮＤ）に対する特定原子面の集積の測定とは大きく異なり、三次元方向のより完全に近い結晶方位情報がより高い分解能で得られるため、曲げ加工性を支配する結晶方位について全く新しい知見を獲得することができる。 The EBSD method was used for the analysis of the crystal orientation in the present invention. EBSD is an abbreviation of Electron Back Scatter Diffraction (Electron Back Scatter Diffraction), which is a reflection electron Kikuchi line diffraction (Kikuchi pattern) generated when a sample is irradiated with an electron beam in a scanning electron microscope (SEM). It is the crystal orientation analysis technology used. In the present invention, a sample area of 500 μm square containing 200 or more crystal grains was scanned at 0.5 μm steps to analyze the orientation.
In the present invention, 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.
Regarding 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 With respect to the azimuth, the rotation angle was calculated around the common rotation axis in (i) and (ii), and the deviation angle was used. For example, with respect to the S orientation (2 3 1) [6-4 3], (1 2 1) [1-1 1] rotates by 19.4 ° with the (20 10 17) direction as the rotation axis. This angle is the offset angle. The common rotation axis is three integers of 40 or less, and among them, one that can be expressed by the smallest deviation angle is adopted. The deviation angle is calculated for all measurement points, and the first decimal place is regarded as an effective number, and each of BR, RDW, Cube, Copper, S, and Brass is 10 degrees or less from the deviation angle. The area of the crystal grain having the orientation of 1 was divided by the total measurement area to obtain the area ratio of the atomic plane of each orientation.
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.
By using EBSD measurement to analyze crystal orientation, it is significantly different from the measurement of accumulation of specific atomic plane to the plate surface direction (ND) by the conventional X-ray diffraction method, and crystal orientation information closer to three-dimensional direction is more complete As it can be obtained with higher resolution, it is possible to obtain a completely new knowledge on the crystal orientation that governs bendability.
　なお、ＥＢＳＤ測定にあたっては、鮮明な菊池線回折像を得るために、機械研磨の後に、コロイダルシリカの砥粒を使用して、基体表面を鏡面研磨した後に、測定を行うことが好ましい。また、測定は板表面から行った。 In the EBSD 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.
（合金組成等）
・Ｎｉ，Ｃｏ，Ｓｉ
　本発明のコネクタ用材料としては、銅または銅合金が用いられる。コネクタに要求される導電性、機械的強度および耐熱性を有するものとして、銅の他に、リン青銅、黄銅、洋白、ベリリウム銅、コルソン系合金（Ｃｕ－Ｎｉ－Ｓｉ系）などの銅合金が好ましい。特に、本発明の特定の結晶方位集積関係を満たす面積率を得たい場合には、純銅系の材料やベリリウム銅、コルソン系合金を含む析出型合金が好ましい。更に、最先端の小型端子材料に求められるような、高強度と高導電性を両立させるためには、Ｃｕ－Ｎｉ－Ｓｉ系、Ｃｕ－Ｎｉ－Ｃｏ－Ｓｉ系、Ｃｕ－Ｃｏ－Ｓｉ系の析出型銅合金が好ましい。
　これは、りん青銅や黄銅などの固溶型合金では、熱処理中の結晶粒成長においてＣｕｂｅ方位粒成長の核となる、冷間圧延材中のＣｕｂｅ方位をもつ微少領域が減少するためである。これは、りん青銅や黄銅などの積層欠陥エネルギーが低い系では、冷間圧延中に剪断帯が発達し易いためである。 (Alloy composition etc.)
・ Ni, Co, Si
Copper or a copper alloy is used as the connector material of the present invention. In addition to copper, 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. In particular, when it is desired to obtain an area ratio satisfying the specific crystal orientation accumulation relationship of the present invention, a precipitation type alloy containing pure copper material, beryllium copper, or Corson alloy is preferable. Furthermore, in order to achieve both high strength and high conductivity, as required for leading-edge small-sized terminal materials, Cu-Ni-Si, Cu-Ni-Co-Si, Cu-Co-Si, etc. 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.
　本発明において、銅（Ｃｕ）に添加する第１の添加元素群であるニッケル（Ｎｉ）とコバルト（Ｃｏ）とケイ素（Ｓｉ）について、それぞれの添加量を制御することにより、Ｎｉ－Ｓｉ、Ｃｏ－Ｓｉ、Ｎｉ－Ｃｏ－Ｓｉの化合物を析出させて銅合金の強度を向上させることができる。その添加量は、ＮｉとＣｏのいずれか１種または２種を合計で、好ましくは０．５～５．０ｍａｓｓ％、さらに好ましくは０．６～４．５ｍａｓｓ％、より好ましくは０．８～４．０ｍａｓｓ％である。Ｎｉの添加量は好ましくは１．５～４．２ｍａｓｓ％、さらに好ましくは１．８～３．９ｍａｓｓ％であり、一方、Ｃｏの添加量は好ましくは０．３～１．８ｍａｓｓ％、さらに好ましくは０．５～１．５ｍａｓｓ％である。特に導電率を高めたい場合は、Ｃｏを必須とすることが好ましい。これらの元素の合計の添加量が多すぎると導電率を低下させ、また、少なすぎると強度が不足する。また、Ｓｉの含有量は好ましくは０．１～１．５ｍａｓｓ％、さらに好ましくは０．２～１．２ｍａｓｓ％である。なお、Ｃｏは希少元素であるとともに、添加量によって溶体化温度を高めるため、用途に応じて顕著に導電性を高める必要が無い場合は、添加しないことが好ましい。 In the present invention, 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%. In particular, when it is desired to increase the conductivity, it is preferable to make Co essential. When the total addition amount of these elements is too large, the conductivity is lowered, and when too small, the strength is insufficient. The content of Si is preferably 0.1 to 1.5 mass%, more preferably 0.2 to 1.2 mass%. In addition, 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.
・その他の元素
　次に、耐応力緩和特性などの特性（二次特性）を向上させる添加元素の効果について示す。好ましい添加元素としては、Ｓｎ、Ｚｎ、Ａｇ、Ｍｎ、Ｂ、Ｐ、Ｍｇ、Ｃｒ、Ｆｅ、Ｔｉ、ＺｒおよびＨｆが挙げられる。添加効果を充分に活用し、かつ導電率を低下させないためには、総量で０．００５～２．０ｍａｓｓ％であることが好ましく、さらに好ましくは０．０１～１．５ｍａｓｓ％、より好ましくは、０．０３～０．８ｍａｓｓ％である。これらの添加元素が総量で多すぎると導電率を低下させる弊害を生じる。なお、これらの添加元素が総量で少なすぎると、これらの元素を添加した効果がほとんど発揮されない。 -Other elements Next, the effects of the additional elements for improving the characteristics (secondary characteristics) such as stress relaxation resistance are shown. As preferable additive elements, Sn, Zn, Ag, Mn, B, P, Mg, Cr, Fe, Ti, Zr and Hf can be mentioned. In order to make full use of the addition effect and not to reduce the conductivity, 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.
　以下に、各元素の添加効果を示す。Ｍｇ、Ｓｎ、Ｚｎは、Ｃｕ－Ｎｉ－Ｓｉ系、Ｃｕ－Ｎｉ－Ｃｏ－Ｓｉ系、Ｃｕ－Ｃｏ－Ｓｉ系銅合金に添加することで耐応力緩和特性が向上する。それぞれを単独で添加した場合よりも併せて添加した場合に相乗効果によってさらに耐応力緩和特性が向上する。また、半田脆化を著しく改善する効果がある。 Below, the addition effect of each element is shown. By adding Mg, Sn, and Zn to a Cu-Ni-Si-based, Cu-Ni-Co-Si-based, or Cu-Co-Si-based copper alloy, 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.
　Ｍｎ、Ａｇ、Ｂ、Ｐは添加すると熱間加工性を向上させるとともに、強度を向上する。 Addition of Mn, Ag, B, and P improves the hot workability and the strength.
　Ｃｒ、Ｆｅ、Ｔｉ、Ｚｒ、Ｈｆは、主な添加元素であるＮｉやＣｏやＳｉとの化合物や単体で微細に析出し、析出硬化に寄与する。また、化合物として５０～５００ｎｍの大きさで析出し、粒成長を抑制することによって結晶粒径を微細にする効果があり、曲げ加工性を良好にする。 Cr, Fe, Ti, Zr, and Hf finely precipitate in a compound with Ni, Co, or Si, which is a main additive element, or a single substance, and contribute to precipitation hardening. In addition, 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.
　次に、本発明の銅合金板材の製造方法（その結晶方位を制御する方法）について説明する。ここでは、析出型銅合金の板材（条材）を例に挙げて説明するが、固溶型合金材料、希薄系合金材料、純銅系材料に展開することが可能である。
　一般に、析出型銅合金は、均質化熱処理した鋳塊を熱間と冷間の各ステップで薄板化し、７００～１０２０℃の温度範囲で最終溶体化熱処理を行って溶質原子を再固溶させた後に、時効析出熱処理と仕上げ冷間圧延によって必要な強度を満足させるように製造される。時効析出熱処理と仕上げ冷間圧延の条件は、所望の強度及び導電性などの特性に応じて、調整される。銅合金の集合組織については、この一連のステップにおける、最終溶体化熱処理中に起きる再結晶によってそのおおよそが決定し、仕上げ圧延中に起きる方位の回転により、最終的に決定される。 Next, the method for producing a copper alloy sheet material of the present invention (a method for controlling the crystal orientation thereof) will be described. Here, although 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.
In general, 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.
　本発明の銅合金板材の製造方法としては、例えば、所定の合金成分組成から成る銅合金素材を高周波溶解炉により溶解し、これを鋳造して鋳塊を得て［工程１］、該鋳塊を１０２０～７００℃で１０分～１０時間の均質化熱処理に施し［工程２］、１０２０～（Ｐ＋３０）℃の温度範囲で、１パス当り２５％以上の加工率で２パス以上の熱間圧延し［工程３－１］、空冷または水冷によって（Ｐ－３０）℃以下の温度まで冷却し［工程３－２］、（Ｐ―３０）～４００℃の温度範囲で、１パス当り２５％以下の加工率で２パス以上の熱間圧延し［工程３－３］、水冷［工程４］、面削［工程５］、５０～９９％の冷間圧延［工程６］、６００～９００℃で１０秒～５分間保持する熱処理［工程７］、５～５５％の加工率の冷間加工［工程８］、７５０～１０００℃において５秒～１時間保持する最終溶体化熱処理［工程９］を行い、その後、３５０～６００℃において５分間～２０時間の時効析出熱処理［工程１０］、２～４５％の加工率の仕上げ圧延［工程１１］、３００～７００℃で１０秒～２時間保持する調質焼鈍［工程１２］を行うことにより、前記［工程１］～［工程１２］をこの順序で行なうことによって本発明の銅合金板材を得る方法が挙げられる。 As a method for producing a copper alloy sheet material of the present invention, for example, 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. Hot rolling at two or more passes at a processing rate of [step 3-3], water cooling [step 4], facing [step 5], 50 to 99% cold rolling [step 6], 600 to 900 ° C. Heat treatment to hold for 10 seconds to 5 minutes [Step 7], Cold working at a working ratio of 5 to 55% [Step 8 Final solution heat treatment [Step 9] held for 5 seconds to 1 hour at 750 to 1000 ° C., followed by aging precipitation heat treatment [Step 10] for 5 minutes to 20 hours at 350 to 600 ° C., 2 to 45% Performing [Step 1] to [Step 12] in this order by performing finish rolling at a working ratio [Step 11] and temper annealing [Step 12] held at 300 to 700 ° C. for 10 seconds to 2 hours. The method of obtaining the copper alloy board | plate material of this invention by is mentioned.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　本発明の銅合金板材は上記の実施態様の製造方法により製造することが好ましいが、ＥＢＳＤ測定における結晶方位解析において、前記Ｒが規定の条件を満足するならば、上記［工程１］～［工程１２］をこの順にすべて行うことに必ずしも拘束されるものではない。上記の方法に含まれるものではあるが、上記［工程１］～［工程１２］の内、例えば、［工程１０］を最終工程として終了してもよい。あるいは、上記［工程１０］～［工程１２］は、この内１つまたは２つ以上を２回以上繰り返して行うこともできる。例えば、［工程１０］を施す前に、２～４５％の加工率の冷間圧延［工程１１’］を行なってもよい。
　熱間圧延［工程３－３］の終了温度が低い場合には、析出速度が遅くなるため、水冷［工程４］は必ずしも必要ではない。どの温度以下で熱間圧延を終了すれば、水冷が不要になるかは、合金濃度や熱間圧延中の析出量によって異なり、適宜選択すればよい。面削［工程５］は、熱間圧延後の材料表面のスケールによっては、省かれる場合もある。また、酸洗浄などによる溶解によって、スケールを除去しても良い。
　動的再結晶温度以上で行う高温圧延を熱間圧延、室温以上の高温で動的再結晶温度以下の高温圧延を温間圧延と、用語を使い分ける場合もあるが、両者を含めて熱間圧延とするのが一般的である。本発明においても、両者を合わせて熱間圧延と呼ぶ。 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. Although included in the above method, among the above [Step 1] to [Step 12], for example, [Step 10] may be completed as the final step. Alternatively, 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].
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. The temperature below which the hot rolling is finished, water cooling becomes unnecessary depending on the alloy concentration and the amount of precipitation during the hot rolling, and may be appropriately selected. 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.
There are cases where 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.
　本発明の銅合金板材の製造方法においては、前記最終溶体化熱処理において、Ｂｒａｓｓ方位、Ｓ方位及びＣｏｐｐｅｒ方位の面積率を減少させ、ＢＲ方位、ＲＤＷ方位及びＣｕｂｅ方位の面積率を上昇させるためには、鋳塊を均質化後に行う熱間加工（［工程３－１］～［工程３－３］からなる［工程３］）において、上述のような条件を選定することが好ましい。従来の銅合金の一般的な製造方法として、均質化後に行う高温加工は変形抵抗を下げる目的、もしくは析出型合金の場合は大量の析出を抑制する目的で、極力高温での加工が行われてきた。一方、本発明の銅合金板材の製造方法においては、第一熱間圧延ステップとして熱間圧延（［工程３－１］）し、その後に冷却（［工程３－２］）し、第二熱間圧延ステップとして第一ステップよりも低い温度で再熱間圧延（［工程３－３］）することを特徴とする。そして、この第一ステップと第二ステップの温度は、溶質原子が完全に固溶する温度であるＰ℃を用いて規定された特定の温度範囲として規定される。
　第一熱間圧延ステップの温度は、１０２０～（Ｐ＋３０）℃である。この温度が高すぎる場合は高温脆性のために、逆に低すぎる場合は再結晶による鋳塊組織の破壊が生じないために、それぞれ割れが起きる場合がある。好ましくは、１０００～（Ｐ＋５０）℃、更に好ましくは、９８０～（Ｐ＋７０）℃である。
　第二熱間圧延ステップの温度は、（Ｐ―３０）～４００℃である。この温度が高すぎる場合は、通常圧延と同等の組織となり、また逆に低すぎる場合は、中間温度脆性による割れが起きる場合がある。好ましくは（Ｐ－５０）～４５０℃、更に好ましくは、（Ｐ－７０）～５００℃である。
　第一熱間圧延ステップの温度（Ｔ１）は第二熱間圧延ステップの温度（Ｔ２）より高いことが好ましく（Ｔ１＞Ｔ２）、典型的な例として言えば、その差（Ｔ１－Ｔ２）が６０～１００℃であることが好ましく、１００～１４０℃であることがより好ましい。 In the method for producing a copper alloy sheet material according to the present invention, 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. As a general manufacturing method of the conventional copper alloy, 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. The On the other hand, in the method for producing a copper alloy sheet material of the present invention, 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. Then, 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. If this temperature is too high, cracking may occur because if it is too low, fracture of the ingot structure due to recrystallization does not occur because of high temperature brittleness. Preferably, it 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. When 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. Preferably 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.
さらに本発明の製造方法においては、第一熱間圧延ステップと第二熱間圧延ステップの間に冷却工程を設けたことが重要である。冷却到達温度は（Ｐ－３０）℃以下であり、下限は特にないが４５０℃以上であることが実際的である。本冷却工程の意義についてここで示す。Ｐ℃を用いて規定されるＴ１とＴ２の間の温度帯は最も溶質元素の析出が速い温度帯である。一方、この中間温度帯より高温では溶質元素が固溶するため、この中間温度帯より低温では原子の拡散が遅く、析出物の粗大化が軽微である。この中間温度帯で圧延加工を受けた場合は、格子欠陥の増加により更に析出の進行が加速され、サブミクロン前後の大きさの粗大な析出物が生成してしまう。そして、その後の冷間圧延において、この数ミクロン前後の大きさの粗大な析出粒子の周囲には歪みが集中するため、中間溶体化熱処理において、粒子周囲の高歪み領域からランダムな方位の再結晶粒が発生し、所望の方位面積率を得られないことがある。すなわち、本発明で規定する方位面積率を達成するためには、方位のランダム化の原因となる粗大析出粒子の制御が肝要であり、そのためには上記中間温度帯において圧延加工を行わないことが好ましい。 Furthermore, in the manufacturing method of the present invention, it is important to provide a cooling process between the first hot rolling step and the second hot rolling step. 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. On the other hand, since 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. When rolling processing is performed in this intermediate temperature zone, the progress of precipitation is further accelerated by the increase of lattice defects, and coarse precipitates having a size of about submicron are generated. Then, in the subsequent cold rolling, strain is concentrated around the coarse precipitated particles having a size of about several microns, so in the intermediate solution heat treatment, recrystallization of random orientation from the high strain region around the particles Grains may occur and a desired azimuthal area rate may not be obtained. That is, in order to achieve the azimuthal area rate defined in the present invention, it is important to control coarse precipitation particles that cause randomization of the azimuth, and for that purpose, the rolling process is not performed in the above intermediate temperature zone preferable.
　また、本発明の製造方法においては、前記熱間圧延の後に行う中間熱処理が重要な意味を有する。中間熱処理は上述のように冷間圧延の間に温度６００～９００℃で行われるのが好ましい。このように、中間熱処理工程を採用することで、全面が再結晶していない組織が得られる。即ち、圧延材中の結晶方位の中でも、回復の速い結晶方位と遅い結晶方位が存在するために、その差によって不均一に再結晶した組織となる。この意図的に作られる不均一性が、中間再結晶熱処理［工程９］における再結晶集合組織の優先発達を促す。 Further, in the production method of the present invention, 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. Thus, by employing 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].
　溶質原子が完全に固溶する温度Ｐ℃は、下記のような一般的な方法によって求めた。鋳塊を１０００℃で１時間の均質化後、熱間圧延と冷間圧延を施して板材とし、その後にソルトバスにて７００～１０００℃まで１０℃おき３０秒間保持する熱処理の後に水焼き入れを行い、各温度における固溶及び析出の状態を凍結し、導電率を測定した。導電率を固溶元素量の代用特性として使用し、熱処理温度の上昇にともなう導電率の低下が飽和する温度を、完全固溶温度Ｐ℃とした。典型的な導電率変化と、それによって前記温度Ｐ（℃）を決定する方法を模式的に図２に示す。典型例としていえば、温度Ｐは７５０～９５０℃であることが実際的である。 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.
　第一熱間圧延ステップにおける１パス加工率は、２５％以上が好ましい。これが低すぎる場合は鋳造組織の破壊が起きない場合がある。上限は圧延機の仕様によって異なり、特に上限は設けないが、通常は５０％以下である。
　第二熱間圧延ステップにおける１パス加工率は、２５％以下が好ましい。これが高すぎる場合は比較的低温での加工のため、加工割れが生じる場合がある。下限は特に設けないが、作業効率から通常は３％以上である。 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.
　本発明の銅合金板材は、例えば、コネクタ用銅合金板材に要求される特性を満足することができる。特に０．２％耐力については５００ＭＰａ以上（好ましくは６００ＭＰａ以上、特に好ましくは７００ＭＰａ以上）、曲げ加工性については９０°Ｗ曲げ試験においてクラックなく曲げ加工が可能な最小曲げ半径（ｒ：ｍｍ）を板厚（ｔ：ｍｍ）で割った値（ｒ／ｔ）が１以下、導電率については３０％ＩＡＣＳ以上（好ましくは３５％ＩＡＣＳ以上、特に好ましくは４０％ＩＡＣＳ以上）を満足するものであり、さらには、耐応力緩和特性については後述する１５０℃に１０００時間保持する測定方法によって応力緩和率（ＳＲ）３０％以下（好ましくは２５％以下）を満たすこともできる、という良好な特性を実現することができる。 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. In particular, 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). Furthermore, 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.
　以下に、実施例に基づき本発明をさらに詳細に説明するが、本発明はこれに限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
実施例１
　表１－１の合金成分の欄の組成に示すように、少なくともＮｉとＣｏの中から１種または２種を合計で０．５～５．０ｍａｓｓ％、Ｓｉを０．１～１．５ｍａｓｓ％含有し、残部がＣｕと不可避不純物から成る合金を高周波溶解炉により溶解し、これを鋳造して鋳塊を得た。この状態を提供材とし、下記Ａ～Ｆのいずれかの工程にて、本発明例１－１～１－１９及び比較例１－１～１－９の銅合金板材の供試材を製造した。 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. .
（工程Ａ）
　１０２０～７００℃で１０分～１０時間の均質化熱処理、１０２０～（Ｐ＋３０）℃の温度範囲で２５％以上の加工率で３パスの熱間圧延、空冷、（Ｐ－３０）～４００℃の温度範囲で２５％以下の加工率で３パスの熱間圧延、水冷、５０～９９％の冷間圧延、６００～９００℃で１０秒～５分間保持する熱処理、５～５５％の加工率の冷間加工、７５０～１０００℃において５秒～１時間保持する最終溶体化熱処理を行う。その後、３５０～６００℃において５分間～２０時間の時効析出熱処理、２～４５％の加工率の仕上げ圧延、３００～７００℃で１０秒～２時間保持する調質焼鈍を行う。 (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.
（工程Ｂ）
　１０２０～７００℃で１０分～１０時間の均質化熱処理、１０２０～（Ｐ＋３０）℃の温度範囲で２５％以上の加工率で３パスの熱間圧延、空冷、（Ｐ－３０）～４００℃の温度範囲で２５％以下の加工率で３パスの熱間圧延、水冷、５０～９９％の冷間圧延、６００～９００℃で１０秒～５分間保持する熱処理、５～５５％の加工率の冷間加工、７５０～１０００℃において５秒～１時間保持する最終溶体化熱処理を行う。その後、２～４５％の加工率の圧延、３５０～６００℃において５分間～２０時間の時効析出熱処理、２～４５％の加工率の仕上げ圧延、３００～７００℃で１０秒～２時間保持する調質焼鈍を行う。 (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.
（工程Ｃ）
　１０２０～７００℃で１０分～１０時間の均質化熱処理、１０２０～（Ｐ＋３０）℃の温度範囲で２５％以上の加工率で３パスの熱間圧延、空冷、（Ｐ－３０）～４００℃の温度範囲で２５％以下の加工率で３パスの熱間圧延、水冷、５０～９９％の冷間圧延、６００～９００℃で１０秒～５分間保持する熱処理、５～５５％の加工率の冷間加工、７５０～１０００℃において５秒～１時間保持する最終溶体化熱処理を行う。その後、３５０～６００℃において５分間～２０時間の時効析出熱処理を行う。 (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.
（工程Ｄ）
　１０２０～７００℃で１０分～１０時間の均質化熱処理、１０２０～（Ｐ＋３０）℃の温度範囲で２５％以上の加工率で３パスの熱間圧延、空冷、（Ｐ－３０）～４００℃の温度範囲で２５％以下の加工率で３パスの熱間圧延、水冷、５０～９９％の冷間圧延、６００～９００℃で１０秒～５分間保持する熱処理、５～５５％の加工率の冷間加工、７５０～１０００℃において５秒～１時間保持する最終溶体化熱処理を行う。その後、２～４５％の加工率の圧延、３５０～６００℃において５分間～２０時間の時効析出熱処理を行う。 (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.
（工程Ｅ）
　１０２０～７００℃で１０分～１０時間の均質化熱処理、１０２０～（Ｐ＋３０）℃の温度範囲で２５％以上の加工率で３パスの熱間圧延、空冷、（Ｐ－３０）～４００℃の温度範囲で２５％以下の加工率で３パスの熱間圧延、水冷、５０～９９％の冷間圧延、７５０～１０００℃において５秒～１時間保持する最終溶体化熱処理を行う。その後、３５０～６００℃において５分間～２０時間の時効析出熱処理、２～４５％の加工率の仕上げ圧延、３００～７００℃で１０秒～２時間保持する調質焼鈍を行う。 (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. 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.
（工程Ｆ）
　１０２０～７００℃で１０分～１０時間の均質化熱処理、１０２０～（Ｐ＋３０）℃の温度範囲で２５％以上の加工率で３パスの熱間圧延、水冷、５０～９９％の冷間圧延、６００～９００℃で１０秒～５分間保持する熱処理、５～５５％の加工率の冷間加工、７５０～１０００℃において５秒～１時間保持する最終溶体化熱処理を行う。その後、３５０～６００℃において５分間～２０時間の時効析出熱処理、２～４５％の加工率の仕上げ圧延、３００～７００℃で１０秒～２時間保持する調質焼鈍を行う。 (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.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　なお、各熱処理や圧延の後に、材料表面の酸化や粗度の状態に応じて酸洗浄や表面研磨を、形状に応じてテンションレベラーによる矯正を行った。 After each heat treatment and rolling, acid cleaning and surface polishing were performed according to the state of oxidation and roughness of the material surface, and correction with a tension leveler was performed according to the shape.
　この供試材について下記の特性調査を行った。ここで、供試材の厚さは０．１５ｍｍとした。本発明例の結果を表１－１に、比較例の結果を表１－２に、それぞれ示す。 The following characteristic investigations were conducted on this test material. Here, the thickness of the test material was 0.15 mm. The results of Examples of the present invention are shown in Table 1-1, and the results of Comparative Example are shown in Table 1-2.
ａ．ＢＲ方位、ＲＤＷ方位、Ｃｕｂｅ方位、Ｃｏｐｐｅｒ方位、Ｓ方位、Ｂｒａｓｓ方位の領域の面積率：
　ＥＢＳＤ法により、約５００μｍ四方の測定領域で、スキャンステップが０．５μｍの条件で測定を行った。測定面積は結晶粒を２００個以上含むことを基準として調整した。上述したように、各理想方位から１０°以下のずれ角度を有する結晶粒の原子面について、各方位を有する原子面の面積を求めて、さらに面積率（Ｒ）を下記式
Ｒ＝（［ＢＲ］＋［ＲＤＷ］＋［Ｗ］）／（［Ｃ］＋［Ｓ］＋［Ｂ］）
によって算出した。 a. Area ratio of area of BR orientation, RDW orientation, Cube orientation, Copper orientation, S orientation, Brass orientation:
According to the EBSD method, measurement was performed under the condition of a scan step of 0.5 μm in a measurement area of about 500 μm. The measurement area was adjusted on the basis of containing 200 or more crystal grains. As described above, for the atomic plane of the crystal grain having a deviation angle of 10 ° or less from each ideal orientation, the area of the atomic plane having each orientation is determined, and the area ratio (R) is ] + [RDW] + [W] / ([C] + [S] + [B])
Calculated by
ｂ．曲げ加工性：
　圧延方向に垂直に幅１０ｍｍ、長さ２５ｍｍに切出し、これに曲げの軸が圧延方向に直角になるようにＷ曲げしたものをＧＷ（Ｇｏｏｄ　Ｗａｙ）、圧延方向に平行になるようにＷ曲げしたものをＢＷ（Ｂａｄ　Ｗａｙ）とし、曲げ部を５０倍の光学顕微鏡で観察し、クラックの有無を調査した。
　曲げ加工部にクラックがなく、シワも軽微なものを「良（◎）」、クラックがないがシワが大きいものの実用上問題ないものを「可（○）」、クラックのあるものを「不可（×）」と判定した。各曲げ部の曲げ角度は９０°、曲げ部の内側半径は０．１５ｍｍとした。 b. Bending workability:
Cut into a width of 10 mm and a length of 25 mm perpendicular to the rolling direction, and W-curved so that the bending axis is perpendicular to the rolling direction is GW (Good Way), W-parallel to the rolling direction The thing was made into BW (Bad Way), the bending part was observed with the optical microscope of 50 time, and the presence or absence of the crack was investigated.
There are no cracks in the bent portion and slight wrinkles as “Good (◎)”, those with no cracks but large wrinkles but with no practical problems “Good (○)”, those with cracks “No ( ×) ". The bending angle of each bent portion was 90 °, and the inner radius of the bent portion was 0.15 mm.
ｃ．０．２％耐力　［ＹＳ］：
　圧延平行方向から切り出したＪＩＳ　Ｚ　２２０１－１３Ｂ号の試験片をＪＩＳ　Ｚ　２２４１に準じて３本測定しその平均値を示した。 c. 0.2% proof stress [YS]:
Three test pieces of JIS Z 2201-13B cut out from the rolling parallel direction were measured according to JIS Z 2241 and the average value was shown.
ｄ：導電率　［ＥＣ］：
　２０℃（±０．５℃）に保たれた恒温漕中で四端子法により比抵抗を計測して導電率を算出した。なお、端子間距離は１００ｍｍとした。 d: conductivity [EC]:
The resistivity was measured by the four-terminal method in a constant temperature oven maintained at 20 ° C. (± 0.5 ° C.) to calculate the conductivity. In addition, the distance between terminals was 100 mm.
ｅ．応力緩和率　［ＳＲ］：
　日本伸銅協会　ＪＣＢＡ　Ｔ３０９：２００１（これは仮規格である。旧規格は「日本電子材料工業会標準規格　ＥＭＡＳ－３００３」であった。）に準じ、以下に示すように、１５０℃で１０００時間保持後の条件で測定した。片持ち梁法により耐力の８０％の初期応力を負荷した。 e. Stress relaxation rate [SR]:
Japan Copper and Brass Association JCBA T309: 2001 (This is a temporary standard. The old standard was "Standard Specification of Japan Electronic Materials Industry Association EMAS-3003".) As shown below, 1000 hours at 150 ° C. It measured on the conditions after holding | maintenance. An initial stress of 80% of the proof stress was applied by the cantilever method.
　図１は耐応力緩和特性の試験方法の説明図であり、（ａ）は熱処理前、（ｂ）は熱処理後の状態である。図１（ａ）に示すように、試験台４に片持ちで保持した試験片１に、耐力の８０％の初期応力を付与した時の試験片１の位置は、基準からδ０の距離である。これを１５０℃の恒温槽に１０００時間保持（前記試験片１の状態での熱処理）し、負荷を除いた後の試験片２の位置は、図１（ｂ）に示すように基準からＨｔの距離である。３は応力を負荷しなかった場合の試験片であり、その位置は基準からＨ１の距離である。この関係から、応力緩和率（％）は（Ｈｔ－Ｈ１）／（δ０－Ｈ１）×１００と算出した。式中、δ０は、基準から試験片１までの距離であり、Ｈ１は、基準から試験片３までの距離であり、Ｈｔは、基準から試験片２までの距離である。 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. As shown in 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 δ 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. From this relationship, the stress relaxation rate (%) was calculated as (H t -H 1 ) / (δ 0 -H 1 ) × 100. Where δ 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, and H t is the distance from the reference to the test specimen 2.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表１―１に示すように、本発明例１－１～１－１９は、曲げ加工性、耐力、導電率、耐応力緩和特性に優れた。
　一方、表１－２に示すように、本発明の規定を満たさない場合は、特性が劣る結果となった。
　すなわち、比較例１－１は、ＮｉとＣｏの総量が少ないために、析出硬化に寄与する化合物（析出物）の密度が低下し強度が劣った。また、ＮｉまたはＣｏと化合物を形成しないＳｉが金属組織中に過剰に固溶し導電率が劣った。比較例１－２は、ＮｉとＣｏの総量が多いために、導電率が劣った。比較例１－３は、Ｓｉが少ないために強度が劣った。比較例１－４は、Ｓｉが多いために導電率が劣った。比較例１－５～１－９はＲが低く、曲げ加工性が劣った。 As shown in Table 1-1, inventive examples 1-1 to 1-19 were excellent in bending workability, proof stress, conductivity, and stress relaxation resistance.
On the other hand, as shown in 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.
実施例２
　表２の合金成分の欄に示す組成で、残部がＣｕと不可避不純物からなる銅合金について、実施例１と同様にして、本発明例２－１～２－１７および比較例２－１～２－３の銅合金板材の供試材を製造し、実施例１と同様に特性を調査した。結果を表２に示す。 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.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表２に示すように、本発明例２－１～本発明例２－１７は、曲げ加工性、耐力、導電率、耐応力緩和特性に優れた。
　一方、本発明の規定を満たさない場合は、特性が劣った。すなわち、比較例２－１、２－２、２－３（いずれも、前記（３）項に係る発明の比較例）は、Ｎｉ、ＣｏおよびＳｉ以外のその他の元素の添加量が多いために、導電率が劣った。 As 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.
実施例３
　表３に示す組成で、残部がＣｕと不可避不純物からなる銅合金について、鋳塊を１０２０～７００℃で１０分～１０時間の均質化熱処理後、表４に示す熱間圧延の後に水冷し、面削、５０～９９％の冷間圧延、６００～９００℃で１０秒～５分間保持する熱処理、５～５５％の加工率の冷間加工、７５０～１０００℃において５秒～１時間保持する最終溶体化熱処理を行う。その後、３５０～６００℃において５分間～２０時間の時効析出熱処理、２～４５％の加工率の仕上げ圧延、３００～７００℃で１０秒～２時間保持する調質焼鈍を行い、供試材を製造した。実施例１と同様に特性を調査した。結果を表４に示す。 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.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　表４に示すように、本発明例３－１～本発明例３－４は、曲げ加工性、耐力、導電率、耐応力緩和特性に優れた。
　一方、本発明の規定を満たさない場合は、特性が劣った。すなわち、比較例３－１～３－４は、熱間加工の条件が本発明で規定する条件を外れたために本発明で規定するＲが所定の値を満足せず、曲げ性が劣った。 As 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.
　このように、本発明により、例えばコネクタ材などの車載部品や電気・電子機器の材料（特にその基体材料）として非常に好適な特性が実現可能である。 As described above, according to the present invention, it is possible to realize very suitable characteristics as a material of an on-vehicle component such as a connector material or a material of an electric / electronic device (in particular, a base material thereof).
　つづいて、従来の製造条件により製造した銅合金板材について、本願発明に係る銅合金板材との相違を明確化するために、その条件で銅合金板材を作製し、上記と同様の特性項目の評価を行った。なお、各板材の厚さは特に断らない限り上記実施例と同じ厚さになるように加工率を調整した。 Then, in order to clarify the difference with the copper alloy plate material concerning the present invention about the copper alloy plate material manufactured according to the conventional manufacturing conditions, a copper alloy plate material is produced under the conditions, and evaluation of the same characteristic items as above Did. The working ratio was adjusted so that the thickness of each plate was the same as that in the above-mentioned embodiment unless otherwise specified.
（比較例１０１）・・・特開２００９－００７６６６号公報の条件
　上記本発明例１－１と同様の金属元素を配合し、残部がＣｕと不可避不純物から成る合金を高周波溶解炉により溶解し、これを０．１～１００℃／秒の冷却速度で鋳造して鋳塊を得た。これを９００～１０２０℃で３分から１０時間の保持後、熱間加工を行った後に水焼き入れを行い、酸化スケール除去のために面削を行った。この後の工程は、次に記載する工程Ａ－３、Ｂ－３の処理を施すことによって銅合金ｃ０１を製造した。
　製造工程には、１回または２回以上の溶体化熱処理を含み、ここでは、その中の最後の溶体化熱処理の前後で工程を分類し、中間溶体化までの工程でＡ－３工程とし、中間溶体化より後の工程でＢ－３工程とした。なお、熱間加工の加工率及びパス回数は、本願出願当時に一般的であった、８００～１０２０℃、１パス加工率３５～４０％、パス回数２～５回という条件を採用した。 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. As 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.
工程Ａ－３：断面減少率が２０％以上の冷間加工を施し、３５０～７５０℃で５分～１０時間の熱処理を施し、断面減少率が５～５０％の冷間加工を施し、８００～１０００℃で５秒～３０分の溶体化熱処理を施す。
工程Ｂ－３：断面減少率が５０％以下の冷間加工を施し、４００～７００℃で５分～１０時間の熱処理を施し、断面減少率が３０％以下の冷間加工を施し、２００～５５０℃で５秒～１０時間の調質焼鈍を施す。 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.
　得られた試験体ｃ０１は、上記実施例とは製造条件について熱間圧延条件の本願における第二熱間圧延ステップの有無の点で異なり、Ｒが低いために曲げ加工性について要求特性を満たさない結果となった。 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.
（比較例１０２）・・・特開平１１－３３５７５６号公報の条件
　上記本発明例１－１と同じ成分組成の銅合金を、クリプトル炉にて木炭被覆下で大気溶解し、ブックモールドに鋳造し、５０ｍｍ×８０ｍｍ×２００ｍｍの鋳塊を作製した。この鋳塊を９３０℃に加熱して厚さ１５ｍｍまで熱間圧延後、直ちに水中急冷した。この熱延材の表面の酸化スケールを除去するため、表面をグラインダで切削した。これを冷間圧延した後、７５０℃で２０秒の熱処理、３０％の冷間圧延、４８０℃で２時間の析出焼鈍を施し、板厚を調整した材料を得て、試験に供した（ｃ０２）。なお、熱間圧延の加工率及びパス回数は、本願出願当時に一般的であった、加工率３５～４０％、パス回数２～５回という条件を採用した。 (Comparative Example 102) Condition of JP-A-11-335756 The copper alloy having the same composition as that of the above-mentioned inventive example 1-1 was dissolved in the air under charcoal coating in a krypton furnace and cast in a book mold , 50 mm × 80 mm × 200 mm were produced. The ingot was heated to 930 ° C., hot rolled to a thickness of 15 mm, and immediately quenched in water. In order to remove the oxide scale of the surface of this hot-rolled material, the surface was ground with a grinder. After cold rolling this, heat treatment at 750 ° C. for 20 seconds, cold rolling at 30%, precipitation annealing at 480 ° C. for 2 hours were carried out to obtain a material having a adjusted plate thickness, which was subjected to a test (c02 ). As the working ratio and the number of passes of hot rolling, the conditions of 35 to 40% working ratio and 2 to 5 passes were adopted, which were common at the time of filing of the present application.
　得られた試験体ｃ０２は、上記実施例とは製造条件について本願における熱処理［工程７］と冷間加工［工程８］の有無及び熱間圧延条件の本願における第二熱間圧延ステップの有無の点で異なり、Ｒが低いために曲げ加工性を満たさない結果となった。 The obtained 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.
（比較例１０３）・・・特開２００８－２２３１３６号公報の条件
　実施例１に示す銅合金を溶製し、縦型連続鋳造機を用いて鋳造した。得られた鋳片（厚さ１８０ｍｍ）から厚さ５０ｍｍの試料を切り出し、これを９５０℃に加熱したのち抽出して、熱間圧延を開始した。その際、９５０～７００℃の温度域での圧延率が６０％以上となり、かつ７００℃未満の温度域でも圧延が行われるようにパススケジュールを設定した。熱間圧延の最終パス温度は６００～４００℃の間にある。鋳片からのトータルの熱間圧延率は約９０％である。熱間圧延後、表層の酸化層を機械研磨により除去（面削）した。 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).
　次いで、冷間圧延を行った後、溶体化処理に供した。試料表面に取り付けた熱電対により溶体化処理時の温度変化をモニターし、昇温過程における１００℃から７００℃までの昇温時間を求めた。溶体化処理後の平均結晶粒径（双晶境界を結晶粒界とみなさない）が１０～６０μｍとなるように到達温度を合金組成に応じて７００～８５０℃の範囲内で調整し、７００～８５０℃の温度域での保持時間を１０ｓｅｃ～１０ｍｉｎの範囲で調整した。続いて、上記溶体化処理後の板材に対して、圧延率で中間冷間圧延を施し、次いで時効処理を施した。時効処理温度は材温４５０℃とし、時効時間は合金組成に応じて４５０℃の時効で硬さがピークになる時間に調整した。このような合金組成に応じて最適な溶体化処理条件や時効処理時間は予備実験により把握してある。次いで、圧延率で仕上げ冷間圧延を行った。仕上げ冷間圧延を行ったものについては、その後さらに、４００℃の炉中に５ｍｉｎ装入する低温焼鈍を施した。このようにして供試材ｃ０３を得た。なお、必要に応じて途中で面削を行い、供試材の板厚は０.２ｍｍに揃えた。主な製造条件は下記に記載してある。 Next, after cold rolling, it was subjected to solution treatment. The temperature change at the time of solution treatment was monitored by a thermocouple attached to the sample surface, and the temperature rising time from 100 ° C. to 700 ° C. in the temperature rising process was determined. The final temperature is adjusted within the range of 700 to 850 ° C according to the alloy composition so that the average grain size after solution treatment (twin boundaries are not regarded as grain boundaries) is 10 to 60 μm, The holding time in the temperature range of 850 ° C. was adjusted in the range of 10 sec to 10 min. Subsequently, the plate material after the solution treatment was subjected to intermediate cold rolling at a rolling ratio and then subjected to an aging treatment. 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. Then, 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. Thus, a test material c03 was obtained. In addition, 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.
　［特開２００８－２２３１３６　実施例１の条件］
　　７００℃未満～４００℃での熱間圧延率：　　５６％（１パス）
　　溶体化処理前　冷間圧延率：　９２％
　　中間冷間圧延　冷間圧延率：　２０％
　　仕上げ冷間圧延　冷間圧延率：　３０％
　　１００℃から７００℃までの昇温時間：　１０秒 [Conditions of JP-A-2008-223136 Example 1]
Hot rolling reduction at less than 700 ° C to 400 ° C: 56% (1 pass)
Before solution treatment Cold rolling ratio: 92%
Intermediate cold rolling Cold rolling ratio: 20%
Finish cold rolling Cold rolling ratio: 30%
Temperature rising time from 100 ° C to 700 ° C: 10 seconds
　得られた試験体ｃ０３は、上記実施例１とは製造条件について　本願における熱間圧延中の第一ステップと第二ステップの冷却工程の有無及び、第二ステップの加工率及び、本願における熱処理［工程７］と冷間加工［工程８］の有無の点で異なり、Ｒが低いために曲げ加工性　を満たさない結果となった。 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.
（比較例１０４）・・・特開２００８－２２３１３６号公報の比較例の条件
　前記比較例１０３に対して、下記項目の加工条件を下記のとおり変えた以外同様にして、供試材ｃ０４を得た。
　［特開２００８－２２３１３６　比較例１の条件］
　　７００℃未満～４００℃での熱間圧延率：　　１７％（１パス）
　　溶体化処理前　冷間圧延率：　９０％
　　中間冷間圧延　冷間圧延率：　２０％
　　仕上げ冷間圧延　冷間圧延率：　３０％
　　１００℃から７００℃までの昇温時間：　１０秒
　得られた試験体ｃ０４は、上記実施例１とは製造条件について本願における熱間圧延中の第一ステップと第二ステップの冷却工程の有無及び、本願における熱処理［工程７］と冷間加工［工程８］の有無の点で異なり、Ｒが低いために曲げ加工性を満たさない結果となった。 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
[Conditions of JP-A-2008-223136 Comparative Example 1]
Hot rolling reduction at less than 700 ° C to 400 ° C: 17% (1 pass)
Before solution treatment Cold rolling rate: 90%
Intermediate cold rolling Cold rolling ratio: 20%
Finish cold rolling Cold rolling ratio: 30%
Temperature rising time from 100 ° C. to 700 ° C .: 10 seconds 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.
　１　初期応力を付与した時の試験片
　２　負荷を除いた後の試験片
　３　応力を負荷しなかった場合の試験片
　４　試験台 1 Specimen when applied initial stress 2 Specimen after removal of load 3 Specimen when no stress applied 4 Test bench

Claims (7)

  1. 　ＥＢＳＤ（Ｅｌｅｃｔｒｏｎ　Ｂａｃｋ　Ｓｃａｔｔｅｒ　Ｄｉｆｆｒａｃｔｉｏｎ：電子後方散乱回折）測定における結晶方位解析において、ＢＲ方位｛３　６　２｝＜８　５　３＞、ＲＤ－Ｒｏｔａｔｅｄ－Ｃｕｂｅ方位｛０　１　２｝＜１　０　０＞、Ｃｕｂｅ方位｛１　０　０｝＜０　０　１＞、Ｃｏｐｐｅｒ方位｛１　２　１｝＜１　１　１＞、Ｓ方位｛２　３　１｝＜３　４　６＞、Ｂｒａｓｓ方位｛１　１　０｝＜１　１　２＞のそれぞれの集合組織方位成分の面積率を［ＢＲ］、［ＲＤＷ］、［Ｗ］、［Ｃ］、［Ｓ］、［Ｂ］とした時に、
    　　Ｒ＝（［ＢＲ］＋［ＲＤＷ］＋［Ｗ］）／（［Ｃ］＋［Ｓ］＋［Ｂ］）
    と定義されるＲが、１以上であり、耐力が５００ＭＰａ以上、導電率が３０％ＩＡＣＳ以上であることを特徴とする銅合金板材。     In crystal orientation analysis in EBSD (Electron Back Scatter Diffraction: electron backscattering diffraction) measurement, BR orientation {3 6 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 1 2> When the area ratio of each texture orientation component of is set to [BR], [RDW], [W], [C], [S], [B],
    R = ([BR] + [RDW] + [W]) / ([C] + [S] + [B])
    A copper alloy sheet material, wherein R is defined as 1 or more, the proof stress is 500 MPa or more, and the conductivity is 30% IACS or more.
  2. 　ＮｉとＣｏのいずれか１種または２種を合計で０．５～５．０ｍａｓｓ％、Ｓｉを０．１～１．５ｍａｓｓ％含有し、残部が銅及び不可避不純物からなる合金組成を有することを特徴とする請求項１に記載の銅合金板材。 Containing an alloy composition containing 0.5 to 5.0 mass% in total of one or two of Ni and Co and 0.1 to 1.5 mass% of Si, with the balance being copper and unavoidable impurities The copper alloy sheet material according to claim 1, characterized in that:
  3. 　さらに、Ｓｎ、Ｚｎ、Ａｇ、Ｍｎ、Ｂ、Ｐ、Ｍｇ、Ｃｒ、Ｆｅ、Ｔｉ、ＺｒおよびＨｆからなる群から選ばれる少なくとも１種を合計で０．００５～２．０ｍａｓｓ％含有する請求項２に記載の銅合金板材。 Furthermore, a total of 0.005 to 2.0 mass% of at least one selected from the group consisting of Sn, Zn, Ag, Mn, B, P, Mg, Cr, Fe, Ti, Zr and Hf. The copper alloy sheet material described in.
  4. 　コネクタ用材料であることを特徴とする請求項１～３のいずれか１項に記載の銅合金板材。 The copper alloy sheet material according to any one of claims 1 to 3, which is a material for a connector.
  5. 　請求項１～４の銅合金板材からなるコネクタ。 A connector comprising the copper alloy sheet material according to any one of claims 1 to 4.
  6. 　請求項１～請求項５のいずれか１項に記載の銅合金板材を製造する方法であって、前記銅合金を与える合金組成の銅合金に、鋳造［工程１］、均質化熱処理［工程２］、熱間加工［工程３］、冷間圧延［工程６］、熱処理［工程７］、冷間圧延［工程８］、最終溶体化熱処理［工程９］をこの順に施し、その後に、時効析出熱処理［工程１０］を施し、上記熱間加工［工程３］は、溶質原子の完全固溶温度をＰ℃とした場合に、まず１０２０℃以下で（Ｐ＋３０）℃以上の温度において１パス加工率が２５％以上の熱間圧延を２パス以上行った後に、（Ｐ－３０）℃以下まで冷却し、（Ｐ－３０）℃以下で４００℃以上の温度において、１パス加工率が２５％以下の熱間圧延を２パス以上行うことからなることを特徴とする銅合金板材の製造方法。 A method for producing a copper alloy sheet material according to any one of claims 1 to 5, wherein a copper alloy having an alloy composition giving said copper alloy is subjected to casting [step 1], homogenization heat treatment [step 2] ], Hot working [step 3], cold rolling [step 6], heat treatment [step 7], cold rolling [step 8], final solution heat treatment [step 9] in this order, and then aging precipitation Heat treatment [Step 10] is applied, and the above-mentioned hot working [Step 3] is carried out, first assuming that the complete solid solution temperature of solute atoms is P ° C., 1 pass processing rate at 1020 ° C. or less and (P + 30) ° C. or more After two passes or more of hot rolling at 25% or more, the product is cooled to (P-30) ° C or less, and at a temperature of 400 ° C or more at (P-30) ° C or less, the one-pass working ratio is 25% or less Production of a copper alloy sheet material characterized by performing two or more passes of hot rolling in Method.
  7. 　前記時効析出熱処理［工程１０］の後に、冷間圧延［工程１１］、及び調質焼鈍［工程１２］をこの順に施すことを特徴とする請求項６に記載の銅合金材料の製造方法。 The method for producing a copper alloy material according to claim 6, wherein cold rolling [step 11] and temper annealing [step 12] are applied in this order after the aging precipitation heat treatment [step 10].
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