WO2012096351A1 - Cu-co-si-zr alloy material and method for producing same - Google Patents

Cu-co-si-zr alloy material and method for producing same Download PDF

Info

Publication number
WO2012096351A1
WO2012096351A1 PCT/JP2012/050508 JP2012050508W WO2012096351A1 WO 2012096351 A1 WO2012096351 A1 WO 2012096351A1 JP 2012050508 W JP2012050508 W JP 2012050508W WO 2012096351 A1 WO2012096351 A1 WO 2012096351A1
Authority
WO
WIPO (PCT)
Prior art keywords
phase particles
temperature
less
alloy material
solution treatment
Prior art date
Application number
PCT/JP2012/050508
Other languages
French (fr)
Japanese (ja)
Inventor
康弘 岡藤
Original Assignee
Jx日鉱日石金属株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jx日鉱日石金属株式会社 filed Critical Jx日鉱日石金属株式会社
Priority to CN201280005365.2A priority Critical patent/CN103298961B/en
Priority to US13/979,103 priority patent/US20130284323A1/en
Priority to KR1020137021206A priority patent/KR20130122654A/en
Priority to EP12734565.0A priority patent/EP2664685B1/en
Publication of WO2012096351A1 publication Critical patent/WO2012096351A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables

Definitions

  • the present invention relates to a Cu—Co—Si—Zr copper alloy material that is excellent in bending workability and can be made highly conductive, and that is particularly suitable for materials for electronic and electrical devices such as movable connectors.
  • Ni 2 Si, Co 2 Si, etc. are precipitated or crystallized as second phase particles in the matrix by cold rolling and aging heat treatment. I am letting.
  • the solid solution amount of Ni 2 Si is relatively large, a conductivity of 60% IACS or more is difficult to achieve with a Cu—Ni—Si based copper alloy. Therefore, having a amount of solid solution is low Co 2 Si as the main precipitates, Cu-Co-Si system that exhibits a high conductivity, Cu-Co-Si-Zr-based or Cu-Ni-Co-Si based alloy Research Has been.
  • These copper alloys cannot achieve the target strength unless they are sufficiently dissolved and fine precipitates are deposited.
  • various solutions have been studied because when the solution is formed at a high temperature, the crystal becomes coarse and the bending workability deteriorates.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2009-242814 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2008-266787 (Patent Document 2)
  • the crystal grain size is controlled by utilizing the effect of suppressing the crystal grain growth, thereby improving the bending workability.
  • the second phase particles are precipitated in the cooling process of hot working or the temperature rising process of solution heat treatment, and also precipitated by aging precipitation heat treatment after chamfering (Patent Document 1, “0025”, etc.).
  • Patent Document 3 Cu—Co—Si (—Zr) alloy having a specific composition is present in the presence of two different sizes of precipitates. It is described that suppression of crystal grain growth and increase in strength can be obtained.
  • specific target values for preventing the movable connector from becoming large are a conductivity of 60% IACS or higher, a 0.2% proof stress YS of 600 MPa or higher, or a tensile strength TS of 630 MPa or higher.
  • the ratio (MBR / t) of the bending radius R and the plate thickness t at which the crack, which is an index, does not occur is 0.5 or less (0.3 mm plate, Bad Way). This bendability varies depending on the crystal grain size and the size and number of the second phase grains.
  • the crystal grain size for obtaining MBR / t of 0.5 or less with a 0.3 mm thick plate is Cu—Co—.
  • the crystal grains grow by solution treatment, and the size of the crystal grain size is determined by the temperature and time of the solution treatment, the additive element, and the size and number of the second phase particles.
  • Patent Documents 1 and 2 are not essential for Co but target a wide range of second phase particles.
  • the crystal grain size is controlled.
  • it is inferior in conductivity and cannot achieve high current.
  • attention is focused on second-phase particles having a diameter of 50 to 1000 nm because they have an effect of suppressing the growth of recrystallized grains in the solution treatment.
  • Co-based second-phase particles of this size are solidified by solution treatment. It may melt and disappear. Therefore, it is necessary to adjust the solution temperature and time so that the precipitate does not dissolve, and only a Cu—Co—Si—Zr alloy having poor conductivity or bendability can be obtained.
  • the second phase particle precipitate having this range size may be precipitated after solutionization, and does not directly show the effect of controlling the crystal grain size.
  • the second phase particle density on the grain boundaries and the diameter and volume density of the second phase particles are evaluated by observation with a transmission electron microscope (TEM), but the crystal grain size can be controlled to 10 ⁇ m or less. If the second phase is precipitated until the particle is overlapped, there is a possibility that accurate numerical values cannot be grasped due to the overlap of particles.
  • Patent Document 3 also focuses on Co-based second phase particles as having an effect of controlling the growth of the crystal grain size, but the particle sizes are 0.005 to 0.05 ⁇ m and 0.05 to 0 in diameter.
  • the Cu—Co—Si—Zr alloy was inferior in bendability. As described above, since the recent precipitation-strengthened copper alloys have been intended for use in thin plates for electronic components such as lead frames, excellent bending workability with a thick plate of about 0.3 mm has not been studied.
  • the present inventor has made the following invention.
  • a Cu—Co—Si—Zr alloy material having a diameter of 0.20 ⁇ m or more and less than 1.00 ⁇ m, containing 3,000 to 500,000 particles / mm 2, and having an electrical conductivity EC
  • a copper alloy material having a good bending workability of 60% IACS or more and a crystal grain size of 10 ⁇ m or less.
  • the copper alloy material according to (1) containing 10 to 2,000 particles / mm 2 of second phase particles having a diameter of 1.00 ⁇ m to 10.00 ⁇ m.
  • the temperature of the hot heating performed after the casting and before the solution treatment is a temperature higher by 45 ° C. or more than the solution treatment temperature selected below, and cooling from the temperature at the start of hot rolling to 600 ° C.
  • the rate is 100 ° C./min or less, and the solution treatment temperature is selected in the range of (50 ⁇ Cowt% + 775) ° C. or more and (50 ⁇ Cowt% + 825) ° C. or less, according to (1) or (2)
  • the solution treatment temperature is adjusted in order to avoid crystal coarsening, and the hot heating temperature before the solution treatment is also solution treatment. It adjusts so that it may adapt to temperature, the cooling rate after hot heating is also adjusted, and the 2nd phase particle
  • the second phase particles By adjusting the second phase particles, a crystal grain size of 10 ⁇ m or less can be obtained, and practical strength can be achieved in addition to bending workability suitable for a movable connector and conductivity capable of increasing current.
  • the alloy material of the present invention contains 1.0 to 2.5 wt% (hereinafter expressed as% unless otherwise specified), preferably 1.5 to 2.2% Co, 0.2 to 0.7%, Preferably, it contains 0.3 to 0.55% Si.
  • the balance other than the following Zr consists of Cu and unavoidable impurities, but various elements that are usually employed as components to be added to copper alloys by those skilled in the art within the range in which the structure of the present invention can achieve the intended effect, For example, it may further contain Cr, Mg, Mn, Ni, Sn, Zn, P, Ag and the like.
  • the stoichiometric ratio of Co / Si when the second phase particle is Co 2 Si is theoretically 4.2, but in the present invention, it is 3.5 to 5.0, preferably 3.8 to 4 In the range, second phase particles Co 2 Si and Co—Si—Zr compounds suitable for precipitation strengthening and crystal grain size adjustment are formed. If the amount of Co and / or Si is too small, the effect of precipitation strengthening is small. If the amount is too large, the solution is not dissolved and the conductivity is poor. When the second phase particles Co 2 Si are precipitated, a precipitation strengthening effect appears, and after the precipitation, the matrix purity becomes high, so that the conductivity is improved. Furthermore, when a specific amount of second phase particles having a specific size is present, the growth of crystal particles is inhibited and the crystal grain size can be reduced to 10 ⁇ m or less.
  • the alloy material of the present invention contains 0.001 to 0.5 wt%, preferably 0.01 to 0.4%, of Zr, and has improved strength and electrical conductivity. This effect is higher than expected from a Cu—Co—Si only system. If Zr is less than 0.001 wt%, the intended effect of increasing the strength and electrical conductivity cannot be obtained, and if it exceeds 0.5 wt%, coarse silicide is generated and the strength and bending workability are reduced.
  • the crystal grain size of the alloy material of the present invention is 10 ⁇ m or less. When the thickness is 10 ⁇ m or less, good bending workability can be achieved.
  • the copper alloy material of the present invention may have various shapes such as a plate material, a strip material, a wire material, a rod material, and a foil, and may be a movable connector plate material or a strip material, but is not particularly limited.
  • the second phase particles of the present invention are particles that are generated when other elements are contained in copper and that form a phase different from the copper matrix (matrix).
  • the number of second phase particles having a diameter of 50 nm or more can be arbitrarily set to a copper plate rolling parallel section (surface parallel to the rolling surface and parallel to the thickness direction) subjected to electrolytic polishing and pickling etching after mirror finishing by mechanical polishing. It is obtained by measuring the number of particles in the corresponding diameter range from a scanning electron micrograph of one visual field obtained by selecting five locations.
  • the diameter refers to an average value of L1 and L2 by measuring the short diameter (L1) and long diameter (L2) of the particles as shown in FIG.
  • second phase particles of the present invention are Co 2 Si and Co—Si—Zr compounds, but other intermetallic compounds such as Ni 2 Si may be in the range.
  • the elements constituting the second phase particles can be confirmed using, for example, EDX attached to FE-SEM (Japan FEI Co., Ltd. Model XL30SFEG).
  • the second phase particles of 0.20 ⁇ m or more and less than 1.00 ⁇ m are 3,000 to 500,000 particles / mm 2 , preferably 10,000 to 200,000 particles / mm 2 ,
  • the content is preferably 13,000 to 100,000 pieces / mm 2 , and is mainly precipitated after hot rolling and before solution treatment, but may be precipitated by solution treatment.
  • the second phase particles precipitated before the solution treatment suppress the growth of the crystal grain size in the solution treatment, but may be dissolved. Therefore, it is preferable to adjust the solution treatment conditions to suppress the variation in the number as much as possible.
  • the second phase particles having a diameter of 1.00 ⁇ m or more and 10.00 ⁇ m or less are preferably 10 to 2,000 particles / mm 2 , more preferably 20 to 1,000 particles / mm 2 , and most preferably 30 to 500 particles. / Mm 2 contained.
  • the second phase particles in this diameter range can be precipitated by slowing the cooling rate after hot heating, and if necessary, the particle size can be adjusted by first aging treatment.
  • the preferable range of the number of second phase particles having the above-mentioned diameter is also linked to the number of second phase particles of 0.20 ⁇ m or more and less than 1.00 ⁇ m.
  • the alloy material of the present invention preferably contains second phase particles having a diameter of more than 10.00 ⁇ m, preferably 1 piece / mm 2 or less, more preferably 0.01 pieces / mm 2 or less.
  • the second phase particles of 0.05 ⁇ m or more and less than 0.20 ⁇ m are precipitated during hot rolling, subsequent cooling, and first aging treatment, but are almost dissolved in the solution treatment, and the subsequent cooling and (second 2) Precipitates by aging treatment.
  • the second phase particles of less than 0.05 ⁇ m are dissolved in the solution treatment and precipitated in large quantities by the (second) aging treatment. Therefore, these second phase particles do not have an effect of adjusting the crystal grain size, but contribute to strength improvement.
  • the electrical conductivity EC of the alloy material of the present invention is 60% IACS or more, preferably 65% IACS or more. Within this range, it is possible to manufacture components capable of increasing the current.
  • the favorable bending workability in the present invention means a 0.3 mm thick plate having a minimum bending radius MBR / t of 0.5 or less (Bad Way). When the 0.3 mm thick plate has an MBR / t of 0.5 or less, the characteristics required during the manufacture and use of electronic components, particularly movable connectors, are satisfied. In addition, when the alloy material of the present invention is made thinner than 0.3 mm, a better bending workability can be obtained.
  • the 0.2% yield strength YS of the alloy material of the present invention is preferably 600 MPa or more, more preferably 650 MPa or more, and the tensile strength TS is preferably 630 MPa or more, more preferably 660 MPa or more. Within the above range, it is particularly sufficient as a material for electronic parts such as a movable connector plate.
  • the manufacturing method process of the alloy material of the present invention is the same as that of a normal precipitation-strengthened copper alloy, and is melt casting ⁇ (homogenization heat treatment) ⁇ hot rolling ⁇ cooling ⁇ (first aging treatment) ⁇ face cutting ⁇ cold. Rolling ⁇ solution treatment ⁇ cooling ⁇ (cold rolling) ⁇ second aging treatment ⁇ final cold rolling ⁇ (tempered strain relief annealing). The steps in parentheses can be omitted, and the final cold rolling may be performed before aging heat treatment.
  • homogeneous heating treatment and hot rolling are performed after casting, but the homogeneous heating treatment may be heating in hot rolling (in the present specification, heating performed in homogeneous heating and hot rolling is performed.
  • the temperature of the hot heating may be any temperature at which the additive element is substantially dissolved, and specifically, it is 40 ° C. or higher, preferably 45 ° C. or higher from the solution treatment temperature selected below.
  • the upper temperature limit for hot heating is individually defined by the metal composition and equipment, but is usually 1,000 ° C. or lower.
  • the heating time depends on the plate thickness, it is preferably 30 to 500 minutes, and more preferably 60 to 240 minutes. It is preferable that almost all additive elements such as Co and Si dissolve during hot heating.
  • the cooling rate after hot heating is 100 ° C./min or less, preferably 5 to 50 ° C./min.
  • the second phase particles finally having a diameter of 0.20 ⁇ m or more and less than 10.00 ⁇ m are deposited within the target range.
  • the fine second-phase particles have been deposited because they have been rapidly cooled by a water-cooled shower or the like for the purpose of suppressing the coarsening of the second-phase particles.
  • the material is chamfered after cooling, it is preferable to further optionally perform the first aging treatment because the size and number of target second phase particles can be adjusted.
  • the conditions for the first aging treatment are preferably 600 to 800 ° C. and 30 s to 30 h.
  • the temperature of the solution treatment performed after the arbitrary first aging treatment is selected in the range of (50 ⁇ Cowt% + 775) ° C. or more and (50 ⁇ Cowt% + 825) ° C. or less.
  • a preferred treatment time is 30 to 500 s, more preferably 60 to 200 s.
  • the adjusted second phase particles remain and prevent the crystal grain size from increasing, while the finely precipitated Co, Si, and Zr are sufficiently dissolved in the second stage of the second stage.
  • a preferable cooling rate after the solution treatment is 10 ° C./s or more. If it falls below this cooling rate, second phase particles precipitate during cooling, and the amount of solid solution decreases.
  • the upper limit of the cooling rate is not particularly limited, but it can be about 100 ° C./s, for example, when the equipment is generally adopted.
  • the contents of Co, Si and Zr are lower than in the present invention, or when they are not gradually cooled after hot rolling and not subjected to the second aging treatment heating, there are few second phase particles precipitated before the solution treatment.
  • solution treatment is performed on an alloy with few precipitated second phase particles, the crystal grain size becomes coarse at a solution treatment time of more than 1 minute at a high temperature exceeding 850 ° C., so only a short heat treatment of about 30 seconds can be performed.
  • the amount that can actually be dissolved is small, a sufficient precipitation strengthening effect cannot be obtained.
  • the temperature of the second aging treatment after the solution treatment is preferably 450 ° C. to 650 ° C. for 1 to 20 hours. Within this range, the diameter of the second phase particles remaining in the solution treatment can be maintained within the range of the present invention, and the added additive elements that have been solid solution are precipitated as fine second phase particles to enhance the strength. Contribute to.
  • the final rolling degree is preferably 5 to 40%, more preferably 10 to 20%. If it is less than 5%, the strength increase due to work hardening is insufficient, while if it exceeds 40%, the bending workability deteriorates.
  • the second aging heat treatment may be performed at 450 ° C. to 600 ° C. for 1 to 20 hours.
  • the strain relief annealing temperature is preferably 250 to 600 ° C., and the annealing time is preferably 10 s to 1 hour. Within this range, there is no change in the size and number of the second phase particles, and the crystal grain size does not change.
  • An ingot having a thickness of 30 mm was cast into a molten metal made of electrolytic copper, Si, Co, and Zr by changing the amount and type of additive elements. This ingot was heated at the temperature in the table for 3 hours (hot), and formed into a plate having a thickness of 10 mm by hot rolling. Next, the oxide scale on the surface is ground and removed, followed by aging heat treatment for 15 hours, followed by solution treatment with appropriately changing temperature and time, cooling at the cooling temperature in the table, and 1 to 15 at the temperature in the table. Time aging heat treatment was performed, and the final thickness was 0.3 mm by the final cold rolling. The strain relief annealing time is 1 minute.
  • the concentration of the additive element in the copper alloy matrix was analyzed by ICP-mass spectrometry using the sample after the chamfering process.
  • the diameter and number of the second phase particles were determined by mechanically polishing the sample rolling parallel cross section before final cold rolling to finish it into a mirror surface, followed by electrolytic polishing and pickling etching, and using a scanning electron microscope I went to 5 photos.
  • the observation magnifications are (a) 5 ⁇ 10 4 times when 0.05 ⁇ m or more and less than 0.20 ⁇ m, (b) 1 ⁇ 10 4 times when 0.20 ⁇ m or more and less than 1.00 ⁇ m, (c) 1.00 ⁇ m or more and 10.00 ⁇ m.
  • the following are 1 ⁇ 10 3 times (represented in the table as “50-200 nm”, “200-1000 nm” and “1000-10000 nm”, respectively).
  • the average crystal grain size was measured by a cutting method in accordance with JIS H0501.
  • the specific resistance was measured by a four-terminal method in a thermostatic chamber maintained at 20 ° C. ( ⁇ 0.5 ° C.) (distance between terminals: 50 mm).
  • a strip test piece (width 10 mm ⁇ length 30 mm ⁇ thickness 0.3 mm) of TD (Transverse Direction) sampled so that the bending axis is perpendicular to the rolling direction is 90.
  • a W bending test (JIS H3130, Bad Way) was performed, and the minimum bending radius (mm) at which no cracks occurred was defined as MBR (Minimum Bend Radius), and the evaluation was performed based on the ratio MBR / t with the plate thickness t (mm). 0.2% proof stress YS and tensile strength TS were measured three times according to JIS Z 2241 for samples of JIS Z2201-13B cut in the rolling parallel direction, and average values were obtained.
  • Examples 1 to 11 were materials suitable for a movable connector having excellent conductivity, strength, bending workability with a thick plate, and capable of increasing current.
  • Reference Example 22 has the same conditions as in Example 6, but after the solution treatment, cool at the cooling temperature in the table, and finish the final thickness to 0.3 mm by final cold rolling before the aging treatment. The aging treatment was performed for 3 hours at the same temperature, and the tempered strain relief annealing was performed in the same manner. Although the strength was slightly inferior to the physical properties of Example 6, the bendability was improved.
  • Comparative Example 12 since the solution temperature is too high, the second phase particles having a diameter of 0.20 ⁇ m or more and less than 1.00 ⁇ m disappear during the solution heat treatment, and the effect of suppressing crystal growth cannot be exhibited. Becomes larger and the bendability is poor. Comparative Example 13 has a low Co / Si ratio, Comparative Example 14 has a high Co / Si ratio, and none of them obtains precipitation strengthening action due to the fine second phase particles, resulting in low strength, and the solid solution concentration of Co or Si is low. Since it becomes high, conductivity is also inferior.
  • Comparative Example 15 the cooling rate after hot working was too slow, so there were many second phase particles having a diameter of 1.00 ⁇ m or more and less than 10.00 ⁇ m, and the bendability was poor.
  • Comparative Example 16 the cooling rate after hot working is fast, and there are few second phase particles having a diameter of 0.20 ⁇ m or more and less than 1.00 ⁇ m, and the effect of suppressing crystal growth cannot be exhibited, and the bendability is poor.
  • the first aging treatment was performed at a high temperature to compensate for the fact that the cooling rate after hot working was high and the number of second phase particles having a diameter of 0.20 ⁇ m or more and less than 1.00 ⁇ m was small.
  • Second phase particles having a size of less than 00 ⁇ m were precipitated, but the bendability was poor because the crystal grain size was increased by heating at that time. Since Comparative Example 18 has higher hot heating temperature and solution treatment temperature than Example 8, the effect of suppressing crystal growth cannot be exhibited, the crystal grain size becomes large, the bendability is poor, and the conductivity is also Example. Low compared to 8.
  • the solution treatment temperature is lower than that in Example 11, and the amount of the added element dissolved in the solution treatment is reduced, and the strength is low.
  • the Co concentration is high, the solution treatment temperature is relatively high, and the time is long.
  • the number of second phase particles having a diameter of 0.20 ⁇ m or more and less than 1.00 ⁇ m is large, and the bendability is poor.
  • the Co concentration is high and the solution treatment temperature is the same as the hot working temperature, which is a high temperature. Therefore, the effect of suppressing the growth of the crystal grain size cannot be exhibited, and the diameter is 0.20 ⁇ m or more and less than 1.00 ⁇ m.
  • the number of second phase particles is small, the number of second phase particles having a diameter of 1.00 ⁇ m to 10.00 ⁇ m is large, and the bendability is poor.
  • the relationship between the steps of the production method and the disappearance and precipitation of the second phase particles is as follows.
  • the additive element dissolves in the copper.
  • second phase particles of 0.05 ⁇ m or more are precipitated.
  • the second phase particles of 0.05 ⁇ m or more are not precipitated, and a large amount of second phase particles of less than 0.05 ⁇ m are precipitated.
  • the second phase particles having a size of less than 0.20 ⁇ m disappear by solid solution treatment with the temperature adjusted.
  • (A) is a solution treatment condition of the present invention, so that it is a solid solution and becomes a number of about 1/5 to 1/10, and the number does not vary much after the second aging treatment.
  • (b) the number hardly increases or decreases under the solution treatment conditions and the second aging treatment conditions of the present invention.
  • (C) is the hot heating and cooling conditions of the present invention, the number does not change at all before the solution treatment and before the final cold rolling.
  • the copper alloy material of the present invention can achieve practical strength in addition to bendability suitable for a movable connector and conductivity capable of increasing current.
  • L1 minor axis of particle
  • L2 major axis of particle

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Conductive Materials (AREA)

Abstract

The present invention relates to a Cu-Co-Si-Zr alloy material which contains 1.0-2.5 wt% of Co, 0.2-0.7 wt% of Si and 0.001-0.5 wt% of Zr with the elemental ratio Co/Si being 3.5-5.0. The Cu-Co-Si-Zr alloy material contains second phase particles having a diameter of 0.20 μm or more but less than 1.00 μm at a density of 3,000-500,000 particles/mm2, and has a crystal grain size of 10 μm or less, an electrical conductivity of 60% IACS or more and good bending workability. The alloy material can be produced by setting the temperature of heating that is carried out after casting and before a solution heat treatment to a temperature that is higher than the later-described solution heat treatment temperature by 45˚C or more, by setting the cooling rate from the start temperature of hot rolling to 600˚C to 100˚C/min or less, and by selecting the solution heat treatment temperature from (50 × Co wt% + 775)˚C to (50 × Co wt% + 825)˚C (inclusive). The aging treatment after the solution heat treatment is preferably carried out at 450-650˚C for 1-20 hours.

Description

Ｃｕ－Ｃｏ－Ｓｉ－Ｚｒ合金材及びその製造方法Cu—Co—Si—Zr alloy material and method for producing the same
　本発明は、曲げ加工性に優れかつ高導電化可能な電子・電気機器用材料であり、特に可動コネクタ等の電子・電気機器用材料に適したＣｕ－Ｃｏ－Ｓｉ－Ｚｒ銅合金材に関する。 The present invention relates to a Cu—Co—Si—Zr copper alloy material that is excellent in bending workability and can be made highly conductive, and that is particularly suitable for materials for electronic and electrical devices such as movable connectors.
　電子・電気機器用材料には、導電性、強度、曲げ加工性を備えた特性が求められるが、近年、電気電子部品、特に可動コネクタにおいて高電流化要求が高まっている。可動コネクタを大型化させないためには、０．２ｍｍ以上の厚肉でも良好な曲げ性を有し、同時に高い導電率及び強度が確保された材料が必要である。
　従来、導電性を劣化させずに高い強度が達成できる特性を有する析出強化型銅合金として、Ｃｕ－Ｎｉ－Ｓｉ系銅合金、Ｃｕ－Ｃｏ－Ｓｉ系、Ｃｕ－Ｃｏ－Ｓｉ－Ｚｒ系やＣｕ－Ｎｉ－Ｃｏ－Ｓｉ系銅合金が知られている。これら銅合金を製造するには、溶体化処理で添加元素を固溶させた後、冷間圧延、時効熱処理によりマトリックス中に第２相粒子としてＮｉ2ＳｉやＣｏ2Ｓｉ等を析出又は晶析させている。しかし、Ｎｉ2Ｓｉの固溶量は比較的大きいため、６０％ＩＡＣＳ以上の導電率はＣｕ－Ｎｉ－Ｓｉ系銅合金では達成することが難しい。そのため、固溶量が低いＣｏ2Ｓｉを主要析出物として有し、高い導電性を示すＣｕ－Ｃｏ－Ｓｉ系、Ｃｕ－Ｃｏ－Ｓｉ－Ｚｒ系やＣｕ－Ｎｉ－Ｃｏ－Ｓｉ系合金が研究されている。これら銅合金は、充分に固溶させてから微細析出物を析出させないと、目標とする強度を達成できない。しかし、高温で溶体化すると結晶が粗大化し、曲げ加工性が悪くなる等の問題が生じるため、種々の対策が検討されてきた。 Electronic and electrical equipment materials are required to have properties such as electrical conductivity, strength, and bending workability. In recent years, there is an increasing demand for higher currents in electrical and electronic parts, particularly movable connectors. In order not to increase the size of the movable connector, it is necessary to use a material that has good bendability even at a thickness of 0.2 mm or more and at the same time ensures high conductivity and strength.
Conventionally, as a precipitation-strengthening-type copper alloy having characteristics that can achieve high strength without deteriorating conductivity, Cu—Ni—Si based copper alloy, Cu—Co—Si based, Cu—Co—Si—Zr based and Cu -Ni-Co-Si based copper alloys are known. In order to produce these copper alloys, after the additive elements are dissolved in the solution treatment, Ni 2 Si, Co 2 Si, etc. are precipitated or crystallized as second phase particles in the matrix by cold rolling and aging heat treatment. I am letting. However, since the solid solution amount of Ni 2 Si is relatively large, a conductivity of 60% IACS or more is difficult to achieve with a Cu—Ni—Si based copper alloy. Therefore, having a amount of solid solution is low Co 2 Si as the main precipitates, Cu-Co-Si system that exhibits a high conductivity, Cu-Co-Si-Zr-based or Cu-Ni-Co-Si based alloy Research Has been. These copper alloys cannot achieve the target strength unless they are sufficiently dissolved and fine precipitates are deposited. However, various solutions have been studied because when the solution is formed at a high temperature, the crystal becomes coarse and the bending workability deteriorates.
　特開２００９－２４２８１４号（特許文献１）や特開２００８－２６６７８７号（特許文献２）では、リードフレーム等の電気電子部品材料用の析出強化型銅合金を製造するために、第２相粒子により結晶粒成長が抑制される効果を利用して結晶粒径を制御し曲げ加工性を改善している。上記文献では、第２相粒子は熱間加工の冷却過程や溶体化熱処理の昇温過程で析出すると共に、面削後の時効析出熱処理によっても析出される（特許文献１「００２５」等）。また、国際公報第２０１０／０１６４２９号（特許文献３）では、特定の組成をもつＣｕ－Ｃｏ－Ｓｉ（－Ｚｒ）合金で、２種類の大きさの組成の異なる析出物を存在させることで、結晶粒成長の抑制と強度の上昇を得られることが記載されている。 In Japanese Patent Application Laid-Open No. 2009-242814 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2008-266787 (Patent Document 2), in order to produce a precipitation-strengthened copper alloy for electrical and electronic component materials such as a lead frame, Therefore, the crystal grain size is controlled by utilizing the effect of suppressing the crystal grain growth, thereby improving the bending workability. In the above document, the second phase particles are precipitated in the cooling process of hot working or the temperature rising process of solution heat treatment, and also precipitated by aging precipitation heat treatment after chamfering (Patent Document 1, “0025”, etc.). In addition, in International Publication No. 2010/016429 (Patent Document 3), Cu—Co—Si (—Zr) alloy having a specific composition is present in the presence of two different sizes of precipitates. It is described that suppression of crystal grain growth and increase in strength can be obtained.
特開２００９－２４２８１４号公報JP 2009-242814 A 特開２００８－２６６７８７号公報JP 2008-266787 A 国際公開第２０１０／０１６４２９号International Publication No. 2010/016429
　一般に、上記可動コネクタを大型化させないための具体的な目標値は、６０％ＩＡＣＳ以上の導電率、６００ＭＰａ以上の０．２％耐力ＹＳ又は６３０ＭＰａ以上の引張強さＴＳであり、曲げ加工性の指標とされる割れが発生しない限界の曲げ半径Ｒと板厚ｔの比（ＭＢＲ／ｔ）は０．５以下（０．３ｍｍ厚板、Ｂａｄ　Ｗａｙ）である。この曲げ加工性は結晶粒径並びに第２相粒子のサイズ及び個数等によって変化するが、０．３ｍｍ厚板で０．５以下のＭＢＲ／ｔを得るための結晶粒径は、Ｃｕ－Ｃｏ－Ｓｉ系やＣｕ－Ｎｉ－Ｃｏ－Ｓｉ系合金では一般に１０μｍ以下であると考えられる。結晶粒は溶体化処理で成長し、溶体化処理の温度及び時間、添加元素、第２相粒子のサイズや個数によって、結晶粒径のサイズが決定される。 In general, specific target values for preventing the movable connector from becoming large are a conductivity of 60% IACS or higher, a 0.2% proof stress YS of 600 MPa or higher, or a tensile strength TS of 630 MPa or higher. The ratio (MBR / t) of the bending radius R and the plate thickness t at which the crack, which is an index, does not occur is 0.5 or less (0.3 mm plate, Bad Way). This bendability varies depending on the crystal grain size and the size and number of the second phase grains. The crystal grain size for obtaining MBR / t of 0.5 or less with a 0.3 mm thick plate is Cu—Co—. For Si-based and Cu-Ni-Co-Si-based alloys, it is generally considered to be 10 μm or less. The crystal grains grow by solution treatment, and the size of the crystal grain size is determined by the temperature and time of the solution treatment, the additive element, and the size and number of the second phase particles.
　しかし、特許文献１、２はＣｏ必須ではなく広い範囲の第２相粒子を対象としており、特許文献１記載の第２相粒子析出物によって結晶粒径を制御する方法では、結晶粒径は制御できるが導電性に劣り、高電流化が達成できない。特許文献２では溶体化処理において再結晶粒の成長を抑制する効果があるとして直径５０～１０００ｎｍの第２相粒子に着目しているが、このサイズのＣｏ系第２相粒子は溶体化で固溶して消滅してしまうことがある。そのため、析出物が固溶しないように溶体化温度や時間を調整する必要があり、導電性と曲げ性のいずれかに劣るＣｕ－Ｃｏ－Ｓｉ－Ｚｒ合金しか得られなかった。また、この範囲サイズの第２相粒子析出物は溶体化後に析出する可能性もあり、直接的に結晶粒径の制御効果を示すわけではない。なお、同文献では結晶粒界上の第２相粒子密度や第２相粒子の径や体積密度を透過型電子顕微鏡（ＴＥＭ）観察により評価しているが、結晶粒径を１０μｍ以下に制御できるまで第２相を析出させると、粒子が重なったりして正確な数値が把握できない可能性があった。
　また、特許文献３においても結晶粒径の成長を制御する効果があるとしてＣｏ系第２相粒子に着目しているが、その粒子サイズは直径０．００５～０．０５μｍ及び０．０５～０．５μｍであり、そのＣｕ－Ｃｏ－Ｓｉ－Ｚｒ合金は曲げ性の劣るものであった。
　このように、最近の析出強化型銅合金はリードフレーム等の電子部品への薄板利用を目的としてきたため、０．３ｍｍ程度の厚板における優れた曲げ加工性は検討されていなかった。 However, Patent Documents 1 and 2 are not essential for Co but target a wide range of second phase particles. In the method of controlling the crystal grain size by the second phase particle precipitate described in Patent Document 1, the crystal grain size is controlled. However, it is inferior in conductivity and cannot achieve high current. In Patent Document 2, attention is focused on second-phase particles having a diameter of 50 to 1000 nm because they have an effect of suppressing the growth of recrystallized grains in the solution treatment. However, Co-based second-phase particles of this size are solidified by solution treatment. It may melt and disappear. Therefore, it is necessary to adjust the solution temperature and time so that the precipitate does not dissolve, and only a Cu—Co—Si—Zr alloy having poor conductivity or bendability can be obtained. Further, the second phase particle precipitate having this range size may be precipitated after solutionization, and does not directly show the effect of controlling the crystal grain size. In this document, the second phase particle density on the grain boundaries and the diameter and volume density of the second phase particles are evaluated by observation with a transmission electron microscope (TEM), but the crystal grain size can be controlled to 10 μm or less. If the second phase is precipitated until the particle is overlapped, there is a possibility that accurate numerical values cannot be grasped due to the overlap of particles.
Patent Document 3 also focuses on Co-based second phase particles as having an effect of controlling the growth of the crystal grain size, but the particle sizes are 0.005 to 0.05 μm and 0.05 to 0 in diameter. The Cu—Co—Si—Zr alloy was inferior in bendability.
As described above, since the recent precipitation-strengthened copper alloys have been intended for use in thin plates for electronic components such as lead frames, excellent bending workability with a thick plate of about 0.3 mm has not been studied.
　本発明者は、上記課題を解決すべく鋭意研究した結果、下記発明をなすに至った。
（１）１．０～２．５ｗｔ％のＣｏ、０．２～０．７ｗｔ％のＳｉ、０．００１～０．５ｗｔ％のＺｒを含有し、Ｃｏ／Ｓｉの元素比は３．５～５．０であるＣｕ－Ｃｏ－Ｓｉ－Ｚｒ合金材であり、直径０．２０μｍ以上１．００μｍ未満の第２相粒子を３，０００～５００，０００個／ｍｍ2含有し、導電率ＥＣが６０％ＩＡＣＳ以上であり、結晶粒径が１０μｍ以下である、良好な曲げ加工性を有する銅合金材。
（２）直径１．００μｍ以上１０．００μｍ以下の第２相粒子を１０～２，０００個／ｍｍ2含有する（１）記載の銅合金材。
（３）０．２％耐力ＹＳが６００ＭＰａ以上である（１）又は（２）記載の銅合金材。
（４）鋳造後、溶体化処理前に行われる熱間加熱の温度が、下記で選択された溶体化処理温度から４５℃以上高い温度であり、熱間圧延開始時温度から６００℃までの冷却速度が１００℃／分以下であり、溶体化処理温度は、（５０×Ｃｏｗｔ％＋７７５）℃以上（５０×Ｃｏｗｔ％＋８２５）℃以下の範囲で選択される、（１）又は（２）記載の銅合金材の製造方法。
（５）溶体化処理後の時効処理は、４５０～６５０℃で１～２０時間である（４）記載の銅合金材の製造方法。 As a result of intensive studies to solve the above problems, the present inventor has made the following invention.
(1) 1.0 to 2.5 wt% Co, 0.2 to 0.7 wt% Si, 0.001 to 0.5 wt% Zr, and the Co / Si element ratio is 3.5 to A Cu—Co—Si—Zr alloy material having a diameter of 0.20 μm or more and less than 1.00 μm, containing 3,000 to 500,000 particles / mm 2, and having an electrical conductivity EC A copper alloy material having a good bending workability of 60% IACS or more and a crystal grain size of 10 μm or less.
(2) The copper alloy material according to (1), containing 10 to 2,000 particles / mm 2 of second phase particles having a diameter of 1.00 μm to 10.00 μm.
(3) The copper alloy material according to (1) or (2), wherein the 0.2% proof stress YS is 600 MPa or more.
(4) The temperature of the hot heating performed after the casting and before the solution treatment is a temperature higher by 45 ° C. or more than the solution treatment temperature selected below, and cooling from the temperature at the start of hot rolling to 600 ° C. The rate is 100 ° C./min or less, and the solution treatment temperature is selected in the range of (50 × Cowt% + 775) ° C. or more and (50 × Cowt% + 825) ° C. or less, according to (1) or (2) A method for producing a copper alloy material.
(5) The method for producing a copper alloy material according to (4), wherein the aging treatment after the solution treatment is performed at 450 to 650 ° C. for 1 to 20 hours.
　本発明は、特定組成を有するＣｕ－Ｃｏ－Ｓｉ－Ｚｒ合金材の製造において、結晶粗大化を避けるために、溶体化処理温度を調整し、溶体化処理前の熱間加熱温度も溶体化処理温度に適合するように調整し、熱間加熱後の冷却速度も調整して、特定の粒径を有する第２相粒子を特定量析出させている。上記第２相粒子の調整により、１０μｍ以下の結晶粒径を得ることができ、可動コネクタに適した曲げ加工性と、高電流化可能な導電性に加え、実用可能な強度を達成できる。 In the production of a Cu—Co—Si—Zr alloy material having a specific composition, the solution treatment temperature is adjusted in order to avoid crystal coarsening, and the hot heating temperature before the solution treatment is also solution treatment. It adjusts so that it may adapt to temperature, the cooling rate after hot heating is also adjusted, and the 2nd phase particle | grains which have a specific particle size precipitate a specific amount. By adjusting the second phase particles, a crystal grain size of 10 μm or less can be obtained, and practical strength can be achieved in addition to bending workability suitable for a movable connector and conductivity capable of increasing current.
第２相粒子の直径を説明する参考図である。It is a reference figure explaining the diameter of a 2nd phase particle.
（Ｃｕ－Ｃｏ－Ｓｉ－Ｚｒ合金材）
　本発明の合金材は、１．０～２．５ｗｔ％（以下特記しない限り％で示す）、好ましくは１．５～２．２％のＣｏを含有し、０．２～０．７％、好ましくは０．３～０．５５％のＳｉを含有する。好ましくは下記Ｚｒ以外の残部はＣｕ及び不可避的不純物よりなるが、本発明の構成が目的とする効果を達成できる範囲内において、当業者が通常銅合金へ添加する成分として採用する種々の元素、例えばＣｒ、Ｍｇ、Ｍｎ、Ｎｉ、Ｓｎ、Ｚｎ、Ｐ、Ａｇなどを更に含んでも良い。
　第２相粒子がＣｏ2Ｓｉの場合のＣｏ／Ｓｉの化学量論比は、理論的には４．２であるが、本発明では３．５～５．０、好ましくは３．８～４．６であり、その範囲内であると析出強化及び結晶粒径調整に適した第２相粒子Ｃｏ2Ｓｉ及びＣｏ－Ｓｉ－Ｚｒ化合物が形成される。Ｃｏ及び／又はＳｉが少なすぎると析出強化効果が少なく、多すぎると固溶されず導電性にも劣る。第２相粒子Ｃｏ2Ｓｉが析出すると、析出強化効果が表れ、析出後はマトリックス純度が高くなるため導電性が向上する。更に、特定サイズの第２相粒子が特定量存在すると、結晶粒子の成長が阻まれ結晶粒径を１０μｍ以下にすることができる。 (Cu-Co-Si-Zr alloy material)
The alloy material of the present invention contains 1.0 to 2.5 wt% (hereinafter expressed as% unless otherwise specified), preferably 1.5 to 2.2% Co, 0.2 to 0.7%, Preferably, it contains 0.3 to 0.55% Si. Preferably, the balance other than the following Zr consists of Cu and unavoidable impurities, but various elements that are usually employed as components to be added to copper alloys by those skilled in the art within the range in which the structure of the present invention can achieve the intended effect, For example, it may further contain Cr, Mg, Mn, Ni, Sn, Zn, P, Ag and the like.
The stoichiometric ratio of Co / Si when the second phase particle is Co 2 Si is theoretically 4.2, but in the present invention, it is 3.5 to 5.0, preferably 3.8 to 4 In the range, second phase particles Co 2 Si and Co—Si—Zr compounds suitable for precipitation strengthening and crystal grain size adjustment are formed. If the amount of Co and / or Si is too small, the effect of precipitation strengthening is small. If the amount is too large, the solution is not dissolved and the conductivity is poor. When the second phase particles Co 2 Si are precipitated, a precipitation strengthening effect appears, and after the precipitation, the matrix purity becomes high, so that the conductivity is improved. Furthermore, when a specific amount of second phase particles having a specific size is present, the growth of crystal particles is inhibited and the crystal grain size can be reduced to 10 μm or less.
　本発明の合金材は、Ｚｒを０．００１～０．５ｗｔ％、好ましくは０．０１～０．４％含有し、強度及び導電率が向上している。この効果はＣｕ－Ｃｏ－Ｓｉのみの系から予測される以上のレベルである。Ｚｒが０．００１ｗｔ％未満であると目的とする強度や導電率上昇の効果が得られず、０．５ｗｔ％を超えると粗大なシリサイドが生成し、強度や曲げ加工性の低下が生じる。
　本発明の合金材の結晶粒径は１０μｍ以下である。１０μｍ以下であると良好な曲げ加工性が達成できる。
　本発明の銅合金材は、例えば板材、条材、線材、棒材、箔などの種々の形状を有してもよく、可動コネクタ用板材又は条材でもよいが特に限定されるものではない。 The alloy material of the present invention contains 0.001 to 0.5 wt%, preferably 0.01 to 0.4%, of Zr, and has improved strength and electrical conductivity. This effect is higher than expected from a Cu—Co—Si only system. If Zr is less than 0.001 wt%, the intended effect of increasing the strength and electrical conductivity cannot be obtained, and if it exceeds 0.5 wt%, coarse silicide is generated and the strength and bending workability are reduced.
The crystal grain size of the alloy material of the present invention is 10 μm or less. When the thickness is 10 μm or less, good bending workability can be achieved.
The copper alloy material of the present invention may have various shapes such as a plate material, a strip material, a wire material, a rod material, and a foil, and may be a movable connector plate material or a strip material, but is not particularly limited.
（第２相粒子）
　本発明の第２相粒子とは、銅に他の元素が含まれる場合に生成し、銅母相（マトリックス）とは異なる相を形成する粒子をいう。直径５０ｎｍ以上の第２相粒子の数は、機械研磨にて鏡面仕上げした後、電解研磨や酸洗エッチングをした銅板圧延平行断面（圧延面に平行、かつ厚み方向に平行な面）を任意に５箇所選択して得られた１視野の走査電子顕微鏡写真から該当する直径範囲の粒子数を測定して得られる。ここで、直径とは、図１のように粒子の短径（Ｌ１）と長径（Ｌ２）を測定し、Ｌ１とＬ２の平均値をいう。
　本発明の第２相粒子の大部分はＣｏ2ＳｉやＣｏ－Ｓｉ－Ｚｒ化合物であるが、Ｎｉ2Ｓｉ等の他の金属間化合物も直径が範囲内であればよい。第２相粒子を構成する元素は、例えば、ＦＥ－ＳＥＭ（日本ＦＥＩ株式会社型式ＸＬ３０ＳＦＥＧ）に付属のＥＤＸを使用して確認できる。 (Second phase particles)
The second phase particles of the present invention are particles that are generated when other elements are contained in copper and that form a phase different from the copper matrix (matrix). The number of second phase particles having a diameter of 50 nm or more can be arbitrarily set to a copper plate rolling parallel section (surface parallel to the rolling surface and parallel to the thickness direction) subjected to electrolytic polishing and pickling etching after mirror finishing by mechanical polishing. It is obtained by measuring the number of particles in the corresponding diameter range from a scanning electron micrograph of one visual field obtained by selecting five locations. Here, the diameter refers to an average value of L1 and L2 by measuring the short diameter (L1) and long diameter (L2) of the particles as shown in FIG.
Most of the second phase particles of the present invention are Co 2 Si and Co—Si—Zr compounds, but other intermetallic compounds such as Ni 2 Si may be in the range. The elements constituting the second phase particles can be confirmed using, for example, EDX attached to FE-SEM (Japan FEI Co., Ltd. Model XL30SFEG).
　本発明の銅合金材では、０．２０μｍ以上１．００μｍ未満の第２相粒子は、３，０００～５００，０００個／ｍｍ2、好ましくは１０，０００～２００，０００個／ｍｍ2、更に好ましくは１３，０００～１００，０００個／ｍｍ2含有され、主に熱間圧延後、溶体化処理前に析出するが溶体化処理により析出することもある。溶体化処理前に析出した第２相粒子は、溶体化処理において結晶粒径の成長を抑制するが、固溶する恐れもある。従って、溶体化処理条件を調整して数の変動をできるだけ抑えることが好ましい。
　又、直径１．００μｍ以上１０．００μｍ以下の第２相粒子は、好ましくは１０～２，０００個／ｍｍ2、更に好ましくは２０～１，０００個／ｍｍ2、最も好ましくは３０～５００個／ｍｍ2含有される。この直径範囲の第２相粒子は、熱間加熱した後の冷却速度を遅くして析出させ、必要であれば第１時効処理することで粒径が調整できる。上記直径の第２相粒子数の好ましい範囲は、０．２０μｍ以上１．００μｍ未満の第２相粒子の数にも連動する。この範囲であると高温溶体化が可能であり、溶体化処理での結晶粒径の成長が抑制される一方、充分に固溶されたＣｏ、Ｓｉ及びＺｒが後段の（第２）時効処理により微細析出されて、高強度、高導電性、良好な曲げ加工性を達成することができる。しかし、２，０００個／ｍｍ2を超えると曲げ性が低下するため好ましくない。
　上記直径０．２０μｍ以上１．００μｍ未満及び１．００μｍ以上１０．００μｍ以下の第２相粒子の数は、溶体化処理前後及び第２時効処理後も余り変動しないので最終圧延前や最終加工後の試験片で評価できる。 In the copper alloy material of the present invention, the second phase particles of 0.20 μm or more and less than 1.00 μm are 3,000 to 500,000 particles / mm 2 , preferably 10,000 to 200,000 particles / mm 2 , The content is preferably 13,000 to 100,000 pieces / mm 2 , and is mainly precipitated after hot rolling and before solution treatment, but may be precipitated by solution treatment. The second phase particles precipitated before the solution treatment suppress the growth of the crystal grain size in the solution treatment, but may be dissolved. Therefore, it is preferable to adjust the solution treatment conditions to suppress the variation in the number as much as possible.
The second phase particles having a diameter of 1.00 μm or more and 10.00 μm or less are preferably 10 to 2,000 particles / mm 2 , more preferably 20 to 1,000 particles / mm 2 , and most preferably 30 to 500 particles. / Mm 2 contained. The second phase particles in this diameter range can be precipitated by slowing the cooling rate after hot heating, and if necessary, the particle size can be adjusted by first aging treatment. The preferable range of the number of second phase particles having the above-mentioned diameter is also linked to the number of second phase particles of 0.20 μm or more and less than 1.00 μm. Within this range, high-temperature solution treatment is possible, and growth of crystal grain size in the solution treatment is suppressed, while sufficiently solid-solved Co, Si, and Zr are removed by the second (second) aging treatment. By being finely precipitated, high strength, high conductivity, and good bending workability can be achieved. However, if it exceeds 2,000 pieces / mm 2 , the bendability is lowered, which is not preferable.
The number of second phase particles having a diameter of 0.20 μm or more and less than 1.00 μm and 1.00 μm or more and 10.00 μm or less does not change much before and after the solution treatment and after the second aging treatment. It can be evaluated with the test piece.
　直径１０．００μｍを超える第２相粒子が存在すると、微細第２相粒子の析出が阻害されて析出強化効果が得られない。従って、本発明の合金材は直径１０．００μｍを超える第２相粒子を、好ましくは１個／ｍｍ2以下、更に好ましくは０．０１個／ｍｍ2以下しか含有しない。
　０．０５μｍ以上０．２０μｍ未満の第２相粒子は、熱間圧延、その後の冷却、第１時効処理中に析出するが、溶体化処理でほとんど固溶してしまい、その後の冷却及び（第２）時効処理により析出する。０．０５μｍ未満の第２相粒子は、溶体化処理で固溶し、（第２）時効処理により大量に析出する。従って、これらの第２相粒子は、結晶粒径の調整効果は無いが強度向上に寄与する。 When the second phase particles having a diameter exceeding 10.00 μm are present, the precipitation of the fine second phase particles is hindered and the precipitation strengthening effect cannot be obtained. Therefore, the alloy material of the present invention preferably contains second phase particles having a diameter of more than 10.00 μm, preferably 1 piece / mm 2 or less, more preferably 0.01 pieces / mm 2 or less.
The second phase particles of 0.05 μm or more and less than 0.20 μm are precipitated during hot rolling, subsequent cooling, and first aging treatment, but are almost dissolved in the solution treatment, and the subsequent cooling and (second 2) Precipitates by aging treatment. The second phase particles of less than 0.05 μm are dissolved in the solution treatment and precipitated in large quantities by the (second) aging treatment. Therefore, these second phase particles do not have an effect of adjusting the crystal grain size, but contribute to strength improvement.
（合金材の物性）
　本発明の合金材の導電率ＥＣは、６０％ＩＡＣＳ以上、好ましくは６５％ＩＡＣＳ以上である。この範囲であると高電流化可能な部品が製造できる。
　本発明で良好な曲げ加工性とは、０．３ｍｍ厚板で最小曲げ半径ＭＢＲ／ｔが０．５以下（Ｂａｄ　Ｗａｙ）をいう。０．３ｍｍ厚板でＭＢＲ／ｔが０．５以下であると、電子部品、特に可動コネクタの製造、使用時に求められる特性を満たす。なお、本発明の合金材を０．３mm厚よりも薄くした場合にはさらに良好な曲げ加工性が得られる。
　本発明の合金材の０．２％耐力ＹＳは、好ましくは６００ＭＰａ以上であり、更に好ましくは６５０ＭＰａ以上であり、引張り強さＴＳは好ましくは６３０ＭＰａ以上、更に好ましくは６６０ＭＰａ以上である。上記範囲内であると、特に可動コネクタ用板材等の電子部品用材料として充分である。 (Physical properties of alloy materials)
The electrical conductivity EC of the alloy material of the present invention is 60% IACS or more, preferably 65% IACS or more. Within this range, it is possible to manufacture components capable of increasing the current.
The favorable bending workability in the present invention means a 0.3 mm thick plate having a minimum bending radius MBR / t of 0.5 or less (Bad Way). When the 0.3 mm thick plate has an MBR / t of 0.5 or less, the characteristics required during the manufacture and use of electronic components, particularly movable connectors, are satisfied. In addition, when the alloy material of the present invention is made thinner than 0.3 mm, a better bending workability can be obtained.
The 0.2% yield strength YS of the alloy material of the present invention is preferably 600 MPa or more, more preferably 650 MPa or more, and the tensile strength TS is preferably 630 MPa or more, more preferably 660 MPa or more. Within the above range, it is particularly sufficient as a material for electronic parts such as a movable connector plate.
（製造方法）
　本発明の合金材の製造方法工程は、通常の析出強化型銅合金と同様であり、溶解鋳造→（均質化熱処理）→熱間圧延→冷却→（第１時効処理）→面削→冷間圧延→溶体化処理→冷却→（冷間圧延）→第２時効処理→最終冷間圧延→（調質歪取焼鈍）である。なお、括弧内の工程は省略可能であり、最終冷間圧延は時効熱処理前に行っても良い。
　本発明では、鋳造後に均質加熱処理及び熱間圧延が行われるが、均質加熱処理は熱間圧延における加熱でもよい（なお、本件明細書では、均質加熱及び熱間圧延の際に行われる加熱を「熱間加熱」と総称する）。
　熱間加熱の温度は、添加元素がほぼ固溶する温度であれば良く、具体的には下記で選択された溶体化処理温度から４０℃以上、好ましくは４５℃以上高温であると良い。熱間加熱の温度上限は、金属組成及び設備により個々に規定されるが通常は１，０００℃以下である。加熱時間は板厚みにもよるが、好ましくは３０～５００分、更に好ましくは６０～２４０分である。熱間加熱時にはＣｏやＳｉ等の添加元素はほとんど溶解することが好ましい。
　熱間加熱後の冷却速度は、１００℃／ｍｉｎ以下、好ましくは５～５０℃／ｍｉｎである。この冷却速度であると最終的に直径０．２０μｍ以上１０．００μｍ未満となる第２相粒子が目的の範囲で析出する。しかし、従来は第２相粒子の粗大化抑制を目的として水冷シャワー等で急冷されていたため微細な第２相粒子しか析出していなかった。
　冷却後、材料は面削されるが、更に任意で第１時効処理を行うと目的の第２相粒子のサイズ、数を調整できるので好ましい。この第１時効処理の条件は、好ましくは６００～８００℃で３０ｓ～３０ｈである。 (Production method)
The manufacturing method process of the alloy material of the present invention is the same as that of a normal precipitation-strengthened copper alloy, and is melt casting → (homogenization heat treatment) → hot rolling → cooling → (first aging treatment) → face cutting → cold. Rolling → solution treatment → cooling → (cold rolling) → second aging treatment → final cold rolling → (tempered strain relief annealing). The steps in parentheses can be omitted, and the final cold rolling may be performed before aging heat treatment.
In the present invention, homogeneous heating treatment and hot rolling are performed after casting, but the homogeneous heating treatment may be heating in hot rolling (in the present specification, heating performed in homogeneous heating and hot rolling is performed. Collectively referred to as “hot heating”).
The temperature of the hot heating may be any temperature at which the additive element is substantially dissolved, and specifically, it is 40 ° C. or higher, preferably 45 ° C. or higher from the solution treatment temperature selected below. The upper temperature limit for hot heating is individually defined by the metal composition and equipment, but is usually 1,000 ° C. or lower. Although the heating time depends on the plate thickness, it is preferably 30 to 500 minutes, and more preferably 60 to 240 minutes. It is preferable that almost all additive elements such as Co and Si dissolve during hot heating.
The cooling rate after hot heating is 100 ° C./min or less, preferably 5 to 50 ° C./min. At this cooling rate, the second phase particles finally having a diameter of 0.20 μm or more and less than 10.00 μm are deposited within the target range. However, conventionally, only the fine second-phase particles have been deposited because they have been rapidly cooled by a water-cooled shower or the like for the purpose of suppressing the coarsening of the second-phase particles.
Although the material is chamfered after cooling, it is preferable to further optionally perform the first aging treatment because the size and number of target second phase particles can be adjusted. The conditions for the first aging treatment are preferably 600 to 800 ° C. and 30 s to 30 h.
　上記任意の第１時効処理の後に行われる溶体化処理の温度は、（５０×Ｃｏｗｔ％＋７７５）℃以上（５０×Ｃｏｗｔ％＋８２５）℃以下の範囲で選択される。好ましい処理時間は３０～５００ｓ、更に好ましくは６０～２００ｓである。この範囲内であると、調整された第２相粒子が残存して結晶粒径の増大を阻止する一方、微細に析出していたＣｏ、Ｓｉ、Ｚｒは充分に固溶されて後段の第２時効処理により微細な第２相粒子として析出する。
　溶体化処理後の好ましい冷却速度は、１０℃／ｓ以上である。この冷却速度を下回ると冷却中に第２相粒子が析出し、固溶量が低下する。冷却速度の好ましい上限は特にないが、一般に採用されている設備であると、例えば、１００℃／ｓ程度でも可能である。
　本発明よりＣｏ、Ｓｉ及びＺｒ含有量が低かったり、熱間圧延後に徐冷されず、第２時効処理加熱もされない場合、溶体化処理前に析出している第２相粒子は少ない。析出第２相粒子が少ない合金を溶体化処理する場合、８５０℃を超える高温で１分を超える溶体化処理時間では結晶粒径が粗大化してしまうため、３０秒程度の短時間の熱処理しかできず、実際に固溶可能な量が少ないため、充分な析出強化効果を得ることができない。 The temperature of the solution treatment performed after the arbitrary first aging treatment is selected in the range of (50 × Cowt% + 775) ° C. or more and (50 × Cowt% + 825) ° C. or less. A preferred treatment time is 30 to 500 s, more preferably 60 to 200 s. Within this range, the adjusted second phase particles remain and prevent the crystal grain size from increasing, while the finely precipitated Co, Si, and Zr are sufficiently dissolved in the second stage of the second stage. Precipitate as fine second phase particles by aging treatment.
A preferable cooling rate after the solution treatment is 10 ° C./s or more. If it falls below this cooling rate, second phase particles precipitate during cooling, and the amount of solid solution decreases. The upper limit of the cooling rate is not particularly limited, but it can be about 100 ° C./s, for example, when the equipment is generally adopted.
When the contents of Co, Si and Zr are lower than in the present invention, or when they are not gradually cooled after hot rolling and not subjected to the second aging treatment heating, there are few second phase particles precipitated before the solution treatment. When solution treatment is performed on an alloy with few precipitated second phase particles, the crystal grain size becomes coarse at a solution treatment time of more than 1 minute at a high temperature exceeding 850 ° C., so only a short heat treatment of about 30 seconds can be performed. In addition, since the amount that can actually be dissolved is small, a sufficient precipitation strengthening effect cannot be obtained.
　溶体化処理後の第２時効処理の温度は、好ましくは４５０℃～６５０℃で１～２０時間である。この範囲内であると溶体化処理で残っていた第２相粒子の直径は本発明の範囲内に維持できると共に、固溶していた添加元素が微細な第２相粒子として析出して強度強化に寄与する。
　最終圧延加工度は、好ましくは５～４０％、更に好ましくは１０～２０％である。５％未満であると、加工硬化による強度の上昇が不足し、一方、４０％を超えると曲げ加工性が低下する。
　また、最終冷間圧延を第２時効熱処理前に行う場合には、第２時効熱処理を４５０℃～６００℃で１～２０時間行えばよい。
　歪取焼鈍温度は、好ましくは２５０～６００℃であり、焼鈍時間は好ましくは１０ｓ～１時間である。この範囲であると第２相粒子のサイズ、数に変化はなく、結晶粒径も変わらない。 The temperature of the second aging treatment after the solution treatment is preferably 450 ° C. to 650 ° C. for 1 to 20 hours. Within this range, the diameter of the second phase particles remaining in the solution treatment can be maintained within the range of the present invention, and the added additive elements that have been solid solution are precipitated as fine second phase particles to enhance the strength. Contribute to.
The final rolling degree is preferably 5 to 40%, more preferably 10 to 20%. If it is less than 5%, the strength increase due to work hardening is insufficient, while if it exceeds 40%, the bending workability deteriorates.
When the final cold rolling is performed before the second aging heat treatment, the second aging heat treatment may be performed at 450 ° C. to 600 ° C. for 1 to 20 hours.
The strain relief annealing temperature is preferably 250 to 600 ° C., and the annealing time is preferably 10 s to 1 hour. Within this range, there is no change in the size and number of the second phase particles, and the crystal grain size does not change.
（製造）
　電気銅、Ｓｉ、Ｃｏ、Ｚｒを原料とした溶湯に、添加元素の量、種類を変更して添加し、厚みが３０ｍｍのインゴットを鋳造した。このインゴットを表中の温度で３時間（熱間）加熱し、熱間圧延により厚み１０ｍｍの板にした。次に、表面の酸化スケールを研削除去し、１５時間時効熱処理し、その後、温度、時間を適宜変更した溶体化処理を行い、表中の冷却温度で冷却し、表中の温度で１～１５時間時効熱処理を行い、最終の冷間圧延で最終厚みを０．３ｍｍに仕上げた。歪取焼鈍時間は１分である。 (Manufacturing)
An ingot having a thickness of 30 mm was cast into a molten metal made of electrolytic copper, Si, Co, and Zr by changing the amount and type of additive elements. This ingot was heated at the temperature in the table for 3 hours (hot), and formed into a plate having a thickness of 10 mm by hot rolling. Next, the oxide scale on the surface is ground and removed, followed by aging heat treatment for 15 hours, followed by solution treatment with appropriately changing temperature and time, cooling at the cooling temperature in the table, and 1 to 15 at the temperature in the table. Time aging heat treatment was performed, and the final thickness was 0.3 mm by the final cold rolling. The strain relief annealing time is 1 minute.
（評価）
　銅合金母地中の添加元素の濃度を、面削工程後のサンプルを使用してＩＣＰ－質量分析法で分析した。
　第２相粒子の直径及び個数は、最終冷間圧延前のサンプル圧延平行断面を機械研磨して鏡面に仕上げた後、電解研磨や酸洗エッチングをし、走査電子顕微鏡を用いて各倍率の顕微鏡写真５枚に対して行った。観察倍率は、（a）０．０５μｍ以上０．２０μｍ未満は５×１０4倍、（b）０．２０μｍ以上１．００μｍ未満は１×１０4倍、（c）１．００μｍ以上１０．００μｍ以下は１×１０3倍である（それぞれ表中では、「５０－２００ｎｍ」、「２００－１０００ｎｍ」及び「１０００－１００００ｎｍ」と示す）。
　結晶粒径は、ＪＩＳ　Ｈ０５０１に従い切断法にて平均結晶粒径を測定した。
　導電率ＥＣは、２０℃（±０．５℃）に保たれた恒温槽中で四端子法により比抵抗を計測した（端子間距離５０ｍｍ）。 (Evaluation)
The concentration of the additive element in the copper alloy matrix was analyzed by ICP-mass spectrometry using the sample after the chamfering process.
The diameter and number of the second phase particles were determined by mechanically polishing the sample rolling parallel cross section before final cold rolling to finish it into a mirror surface, followed by electrolytic polishing and pickling etching, and using a scanning electron microscope I went to 5 photos. The observation magnifications are (a) 5 × 10 4 times when 0.05 μm or more and less than 0.20 μm, (b) 1 × 10 4 times when 0.20 μm or more and less than 1.00 μm, (c) 1.00 μm or more and 10.00 μm. The following are 1 × 10 3 times (represented in the table as “50-200 nm”, “200-1000 nm” and “1000-10000 nm”, respectively).
As for the crystal grain size, the average crystal grain size was measured by a cutting method in accordance with JIS H0501.
For the electrical conductivity EC, the specific resistance was measured by a four-terminal method in a thermostatic chamber maintained at 20 ° C. (± 0.5 ° C.) (distance between terminals: 50 mm).
　曲げ加工性ＭＢＲ／ｔについては、曲げ軸が圧延方向と直角になるようにしてＴ.Ｄ.(Transverse Direction)採取した短冊試験片（幅１０ｍｍ×長さ３０ｍｍ×厚さ０．３ｍｍ）の９０°Ｗ曲げ試験（ＪＩＳ　Ｈ３１３０、Bad Way）を行い、割れの発生しない最小曲げ半径（ｍｍ）をＭＢＲ(Minimum Bend Radius)とし、板厚ｔ（ｍｍ）との比ＭＢＲ／ｔにより評価した。
　０．２％耐力ＹＳ及び引張強さＴＳは、圧延平行方向に切り出したＪＩＳ Ｚ２２０１－１３Ｂ号のサンプルをＪＩＳ　Ｚ　２２４１に準じて３回測定して平均値を求めた。 With respect to the bending workability MBR / t, a strip test piece (width 10 mm × length 30 mm × thickness 0.3 mm) of TD (Transverse Direction) sampled so that the bending axis is perpendicular to the rolling direction is 90. A W bending test (JIS H3130, Bad Way) was performed, and the minimum bending radius (mm) at which no cracks occurred was defined as MBR (Minimum Bend Radius), and the evaluation was performed based on the ratio MBR / t with the plate thickness t (mm).
0.2% proof stress YS and tensile strength TS were measured three times according to JIS Z 2241 for samples of JIS Z2201-13B cut in the rolling parallel direction, and average values were obtained.
　Ｃｏ及びＳｉ濃度、Ｃｏ／Ｓｉの元素比、直径０．２０μｍ以上１．００μｍ未満の第２相粒子の数、導電率ＥＣ及び結晶粒径を本発明の範囲内として、Ｚｒの添加量を変更した結果を表１Ａ～Ｃに示す。
　表１Ａ及びＢより、Ｚｒを全く添加しない比較例３に比べ、Ｚｒを０．０１％又は０．３％添加した実施例１又は２は強度及び導電率又は導電率が上昇している。しかも、導電率はＺｒ添加量に比例して上昇することが確認された。しかし、１．０％添加した比較例４では強度及び曲げ加工性が低下した（表１Ｃの説明は後記する）。 Co and Si concentration, Co / Si element ratio, number of second phase particles with diameter of 0.20 μm or more and less than 1.00 μm, conductivity EC and crystal grain size are within the scope of the present invention, and the amount of Zr added is changed The results are shown in Tables 1A-C.
From Table 1A and B, compared with the comparative example 3 which does not add Zr at all, Example 1 or 2 which added 0.01% or 0.3% of Zr has an increase in strength and electrical conductivity or electrical conductivity. Moreover, it was confirmed that the conductivity increased in proportion to the amount of Zr added. However, in Comparative Example 4 in which 1.0% was added, the strength and bending workability were lowered (the explanation of Table 1C will be described later).
　上記結果に基づき、Ｚｒ量を０．１%にして成分組成及び製造条件を変化させた結果を表２Ａ～Ｃに示す（表２Ｃの説明は後記する）。
　実施例１～１１は本発明の要件を満たすため、優れた導電性、強度、厚板での曲げ加工性を備え、高電流化可能な可動コネクタに適する材料であった。
　参考例２２は、実施例６と同様の条件であるが、溶体化処理後、表中の冷却温度で冷却し、時効処理前に最終冷間圧延で最終厚みを０．３ｍｍに仕上げ、表中の温度で３時間時効処理を行い、同様に調質歪取り焼鈍したものであり、実施例６の物性と比較して若干強度が劣るものの曲げ性が向上している。 Based on the above results, the results of changing the component composition and the production conditions with the Zr content being 0.1% are shown in Tables 2A to 2C (the description of Table 2C will be described later).
In order to satisfy the requirements of the present invention, Examples 1 to 11 were materials suitable for a movable connector having excellent conductivity, strength, bending workability with a thick plate, and capable of increasing current.
Reference Example 22 has the same conditions as in Example 6, but after the solution treatment, cool at the cooling temperature in the table, and finish the final thickness to 0.3 mm by final cold rolling before the aging treatment. The aging treatment was performed for 3 hours at the same temperature, and the tempered strain relief annealing was performed in the same manner. Although the strength was slightly inferior to the physical properties of Example 6, the bendability was improved.
　比較例１２は、溶体化温度が高すぎるので直径０．２０μｍ以上１．００μｍ未満の第２相粒子が溶体化熱処理中に消滅し、結晶の成長を抑制する効果が発揮できず、結晶粒径が大きくなり曲げ性が悪い。
　比較例１３はＣｏ／Ｓｉ比が低く、比較例１４はＣｏ／Ｓｉ比が高く、いずれも微細第２相粒子による析出強化作用を得られず強度が低くなり、Ｃｏ又はＳｉの固溶濃度が高くなるため導電性も劣る。
　比較例１５は熱間加工後の冷却速度が遅すぎたため、直径１．００μｍ以上１０．００μｍ未満の第２相粒子が多く、曲げ性が悪い。
　比較例１６は、熱間加工後の冷却速度が速く直径０．２０μｍ以上１．００μｍ未満の第２相粒子が少なく結晶の成長を抑制する効果が発揮できず、曲げ性が悪い。比較例１７では、熱間加工後の冷却速度が速く直径０．２０μｍ以上１．００μｍ未満の第２相粒子が少ないのを補うために第１時効処理を高温で行い直径０．２０μｍ以上１．００μｍ未満の第２相粒子を析出させたが、そのときの加熱で結晶粒径が大きくなってしまったため、曲げ性が悪い。
　比較例１８は実施例８に比べ、熱間加熱温度及び溶体化処理温度が高いため、結晶の成長を抑制する効果が発揮できず、結晶粒径が大きくなり曲げ性が悪く導電性も実施例８に比べ低い。
　比較例１９は実施例１１に比べ、溶体化処理温度が低く、溶体化処理で添加元素の固溶量が少なくなり、強度が低い。
　比較例２０はＣｏ濃度が高く、溶体化処理温度が比較的高く時間が長いため直径０．２０μｍ以上１．００μｍ未満の第２相粒子個数が多く、曲げ性が悪い。
　比較例２１はＣｏ濃度が高く、溶体化処理温度が熱間加工温度と同じで高温であるため、結晶粒径の成長を抑制する効果が発揮できず、直径０．２０μｍ以上１．００μｍ未満の第２相粒子個数が少なく直径１．００μｍ以上１０．００μｍ以下の第２相粒子個数が多く、曲げ性が悪い。 In Comparative Example 12, since the solution temperature is too high, the second phase particles having a diameter of 0.20 μm or more and less than 1.00 μm disappear during the solution heat treatment, and the effect of suppressing crystal growth cannot be exhibited. Becomes larger and the bendability is poor.
Comparative Example 13 has a low Co / Si ratio, Comparative Example 14 has a high Co / Si ratio, and none of them obtains precipitation strengthening action due to the fine second phase particles, resulting in low strength, and the solid solution concentration of Co or Si is low. Since it becomes high, conductivity is also inferior.
In Comparative Example 15, the cooling rate after hot working was too slow, so there were many second phase particles having a diameter of 1.00 μm or more and less than 10.00 μm, and the bendability was poor.
In Comparative Example 16, the cooling rate after hot working is fast, and there are few second phase particles having a diameter of 0.20 μm or more and less than 1.00 μm, and the effect of suppressing crystal growth cannot be exhibited, and the bendability is poor. In Comparative Example 17, the first aging treatment was performed at a high temperature to compensate for the fact that the cooling rate after hot working was high and the number of second phase particles having a diameter of 0.20 μm or more and less than 1.00 μm was small. Second phase particles having a size of less than 00 μm were precipitated, but the bendability was poor because the crystal grain size was increased by heating at that time.
Since Comparative Example 18 has higher hot heating temperature and solution treatment temperature than Example 8, the effect of suppressing crystal growth cannot be exhibited, the crystal grain size becomes large, the bendability is poor, and the conductivity is also Example. Low compared to 8.
In Comparative Example 19, the solution treatment temperature is lower than that in Example 11, and the amount of the added element dissolved in the solution treatment is reduced, and the strength is low.
In Comparative Example 20, the Co concentration is high, the solution treatment temperature is relatively high, and the time is long. Therefore, the number of second phase particles having a diameter of 0.20 μm or more and less than 1.00 μm is large, and the bendability is poor.
In Comparative Example 21, the Co concentration is high and the solution treatment temperature is the same as the hot working temperature, which is a high temperature. Therefore, the effect of suppressing the growth of the crystal grain size cannot be exhibited, and the diameter is 0.20 μm or more and less than 1.00 μm. The number of second phase particles is small, the number of second phase particles having a diameter of 1.00 μm to 10.00 μm is large, and the bendability is poor.
　本発明は理論に制限されるわけではないが、製造方法の工程と第２相粒子の消滅、析出の関係は下記の通りであると考えられる。熱間加熱中に添加元素が銅中に固溶する。熱間圧延中及び熱間圧延後の速度を調節した冷却段階では０．０５μｍ以上の第２相粒子が析出する。熱間圧延後の第１時効処理では、０．０５μｍ以上の第２相粒子は析出せず、０．０５μｍ未満の第２相粒子が大量に析出する。温度を調整した溶体化処理で０．２０μｍ未満の第２相粒子が固溶消滅する。溶体化処理後の速度を調節した冷却段階では、主に０．０５μｍ以上０．２μｍ未満の第２相粒子が少量析出する。溶体化処理後の第２時効処理で０．０５μｍ未満の第２相粒子が大量に析出物する。
　表１Ｃ及び表２Ｃに、（ａ）５０ｎｍ以上２００ｎｍ未満、（ｂ）２００ｎｍ以上１０００ｎｍ未満、（ｃ）１．０００ｎｍ以上１０．０００ｎｍの直径範囲の第２相粒子が製造工程においてどのように変化するか測定した結果を示す。なお、全ての測定で直径１０，０００ｎｍ（１０．００μｍ）を超える第２相粒子は確認できなかった。直径が多くなるに従い個数が対数的に少なくなるので、表示桁数を変更している。
　（ａ）は本発明の溶体化処理条件であると固溶して５分の１から１０分の１程度の数になり、第２時効処理後では数にあまり変動はない。（ｂ）は本発明の溶体化処理条件及び第２時効処理条件であると数がほとんど増減しない。（ｃ）は本発明の熱間加熱、冷却条件であると、溶体化処理前も最終冷間圧延前も数が全く変化しない。
　なお、第１時効処理温度が高いと（ｂ）の個数が増大し（比較例１７）、溶体化処理温度が高いか、処理時間が長いと（ｂ）の個数が減少し、本発明の下限値未満になる傾向がある（比較例１８及び２１）。 Although the present invention is not limited by theory, it is considered that the relationship between the steps of the production method and the disappearance and precipitation of the second phase particles is as follows. During the hot heating, the additive element dissolves in the copper. In the cooling stage in which the speed during hot rolling and after hot rolling is adjusted, second phase particles of 0.05 μm or more are precipitated. In the first aging treatment after hot rolling, the second phase particles of 0.05 μm or more are not precipitated, and a large amount of second phase particles of less than 0.05 μm are precipitated. The second phase particles having a size of less than 0.20 μm disappear by solid solution treatment with the temperature adjusted. In the cooling stage in which the speed after the solution treatment is adjusted, a small amount of second phase particles of 0.05 μm or more and less than 0.2 μm mainly precipitate. In the second aging treatment after the solution treatment, a large amount of second phase particles of less than 0.05 μm are precipitated.
Table 1C and Table 2C show how the second phase particles having a diameter range of (a) 50 nm or more and less than 200 nm, (b) 200 nm or more and less than 1000 nm, and (c) 1.000 nm or more and 10.000 nm change in the manufacturing process. The measured results are shown. In all measurements, second phase particles having a diameter exceeding 10,000 nm (10.00 μm) could not be confirmed. Since the number decreases logarithmically as the diameter increases, the number of display digits is changed.
(A) is a solution treatment condition of the present invention, so that it is a solid solution and becomes a number of about 1/5 to 1/10, and the number does not vary much after the second aging treatment. In (b), the number hardly increases or decreases under the solution treatment conditions and the second aging treatment conditions of the present invention. (C) is the hot heating and cooling conditions of the present invention, the number does not change at all before the solution treatment and before the final cold rolling.
When the first aging treatment temperature is high, the number of (b) increases (Comparative Example 17), and when the solution treatment temperature is high or the treatment time is long, the number of (b) decreases, and the lower limit of the present invention. There is a tendency to be less than the value (Comparative Examples 18 and 21).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　本発明の銅合金材により、可動コネクタに適した曲げ加工性と、高電流化可能な導電性に加え、実用可能な強度を達成できる。 The copper alloy material of the present invention can achieve practical strength in addition to bendability suitable for a movable connector and conductivity capable of increasing current.
Ｌ１：粒子の短径
Ｌ２：粒子の長径 L1: minor axis of particle L2: major axis of particle

Claims (5)

  1. 　１．０～２．５ｗｔ％のＣｏ、０．２～０．７ｗｔ％のＳｉ、０．００１～０．５ｗｔ％のＺｒを含有し、Ｃｏ／Ｓｉの元素比は３．５～５．０であるＣｕ－Ｃｏ－Ｓｉ－Ｚｒ合金材であり、直径０．２０μｍ以上１．００μｍ未満の第２相粒子を３，０００～５００，０００個／ｍｍ2含有し、導電率ＥＣが６０％ＩＡＣＳ以上であり、結晶粒径が１０μｍ以下である、良好な曲げ加工性を有する銅合金材。 It contains 1.0 to 2.5 wt% Co, 0.2 to 0.7 wt% Si, 0.001 to 0.5 wt% Zr, and the Co / Si element ratio is 3.5 to 5.0. in which a Cu-Co-Si-Zr alloy, and the second phase particles 3,000 to 500,000 / mm 2 containing less than a diameter of 0.20 [mu] m 1.00 .mu.m, conductivity EC is 60% IACS A copper alloy material having good bending workability and having a crystal grain size of 10 μm or less.
  2. 　直径１．００μｍ以上１０．００μｍ以下の第２相粒子を１０～２，０００個／ｍｍ2含有する請求項１記載の銅合金材。 The copper alloy material according to claim 1, comprising 10 to 2,000 particles / mm 2 of second phase particles having a diameter of 1.00 µm to 10.00 µm.
  3. 　０．２％耐力ＹＳが６００ＭＰａ以上である請求項１又は２記載の銅合金材。 The copper alloy material according to claim 1 or 2, wherein 0.2% proof stress YS is 600 MPa or more.
  4. 　鋳造後、溶体化処理前に行われる熱間加熱の温度が、下記で選択された溶体化処理温度から４５℃以上高い温度であり、熱間圧延開始時温度から６００℃までの冷却速度が１００℃／分以下であり、溶体化処理温度は、（５０×Ｃｏｗｔ％＋７７５）℃以上（５０×Ｃｏｗｔ％＋８２５）℃以下の範囲で選択される、請求項１又は２記載の銅合金材の製造方法。 The temperature of the hot heating performed after the casting and before the solution treatment is 45 ° C. or more higher than the solution treatment temperature selected below, and the cooling rate from the hot rolling start temperature to 600 ° C. is 100 The copper alloy material according to claim 1 or 2, wherein the solution treatment temperature is selected in a range of (50 x Cowt% + 775) ° C or higher and (50 x Cowt% + 825) ° C or lower. Method.
  5. 　溶体化処理後の時効処理は、４５０～６５０℃で１～２０時間である請求項４記載の銅合金材の製造方法。 The method for producing a copper alloy material according to claim 4, wherein the aging treatment after the solution treatment is performed at 450 to 650 ° C for 1 to 20 hours.
PCT/JP2012/050508 2011-01-13 2012-01-12 Cu-co-si-zr alloy material and method for producing same WO2012096351A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201280005365.2A CN103298961B (en) 2011-01-13 2012-01-12 Cu-Co-Si-Zr alloy material and method for producing same
US13/979,103 US20130284323A1 (en) 2011-01-13 2012-01-12 Cu-Co-Si-Zr ALLOY MATERIAL AND MANUFACTURING METHOD THEREOF
KR1020137021206A KR20130122654A (en) 2011-01-13 2012-01-12 Cu-co-si-zr alloy material and method for producing same
EP12734565.0A EP2664685B1 (en) 2011-01-13 2012-01-12 Cu-co-si-zr alloy material and method for producing same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011005088A JP2012144789A (en) 2011-01-13 2011-01-13 Cu-Co-Si-Zr ALLOY MATERIAL
JP2011-005088 2011-01-13

Publications (1)

Publication Number Publication Date
WO2012096351A1 true WO2012096351A1 (en) 2012-07-19

Family

ID=46507242

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/050508 WO2012096351A1 (en) 2011-01-13 2012-01-12 Cu-co-si-zr alloy material and method for producing same

Country Status (7)

Country Link
US (1) US20130284323A1 (en)
EP (1) EP2664685B1 (en)
JP (1) JP2012144789A (en)
KR (1) KR20130122654A (en)
CN (1) CN103298961B (en)
TW (1) TWI432587B (en)
WO (1) WO2012096351A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104388859A (en) * 2014-11-18 2015-03-04 昆明理工大学 Method for simultaneously improving strength and plasticity of copper aluminum alloy
KR102434449B1 (en) * 2018-09-10 2022-08-18 주식회사 엘지화학 Backplate for display apparatus having excellent fatigue resistance properties

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008056977A (en) * 2006-08-30 2008-03-13 Mitsubishi Electric Corp Copper alloy and its production method
JP2008088512A (en) * 2006-10-03 2008-04-17 Nikko Kinzoku Kk Method for producing copper alloy for electronic material
JP2008266787A (en) 2007-03-28 2008-11-06 Furukawa Electric Co Ltd:The Copper alloy material and its manufacturing method
WO2009116649A1 (en) * 2008-03-21 2009-09-24 古河電気工業株式会社 Copper alloy material for electric and electronic components
JP2009242814A (en) 2008-03-28 2009-10-22 Furukawa Electric Co Ltd:The Copper alloy material and producing method thereof
JP2010016429A (en) 2008-07-01 2010-01-21 Sony Corp Howling detector and howling detection method
WO2010016429A1 (en) 2008-08-05 2010-02-11 古河電気工業株式会社 Copper alloy material for electrical/electronic component

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100439530C (en) * 2004-12-24 2008-12-03 株式会社神户制钢所 Copper alloy having bendability and stress relaxation property
JP4357536B2 (en) * 2007-02-16 2009-11-04 株式会社神戸製鋼所 Copper alloy sheet for electrical and electronic parts with excellent strength and formability
KR101570555B1 (en) * 2008-07-31 2015-11-19 후루카와 덴키 고교 가부시키가이샤 Copper alloy material for electrical and electronic components, and manufacturing method therefor
JP5619389B2 (en) * 2008-08-05 2014-11-05 古河電気工業株式会社 Copper alloy material

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008056977A (en) * 2006-08-30 2008-03-13 Mitsubishi Electric Corp Copper alloy and its production method
JP2008088512A (en) * 2006-10-03 2008-04-17 Nikko Kinzoku Kk Method for producing copper alloy for electronic material
JP2008266787A (en) 2007-03-28 2008-11-06 Furukawa Electric Co Ltd:The Copper alloy material and its manufacturing method
WO2009116649A1 (en) * 2008-03-21 2009-09-24 古河電気工業株式会社 Copper alloy material for electric and electronic components
JP2009242814A (en) 2008-03-28 2009-10-22 Furukawa Electric Co Ltd:The Copper alloy material and producing method thereof
JP2010016429A (en) 2008-07-01 2010-01-21 Sony Corp Howling detector and howling detection method
WO2010016429A1 (en) 2008-08-05 2010-02-11 古河電気工業株式会社 Copper alloy material for electrical/electronic component

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2664685A4 *

Also Published As

Publication number Publication date
CN103298961A (en) 2013-09-11
EP2664685B1 (en) 2015-10-07
US20130284323A1 (en) 2013-10-31
JP2012144789A (en) 2012-08-02
EP2664685A4 (en) 2014-04-09
KR20130122654A (en) 2013-11-07
TW201233819A (en) 2012-08-16
TWI432587B (en) 2014-04-01
EP2664685A1 (en) 2013-11-20
CN103298961B (en) 2015-06-17

Similar Documents

Publication Publication Date Title
JP4677505B1 (en) Cu-Ni-Si-Co-based copper alloy for electronic materials and method for producing the same
JP5441876B2 (en) Cu-Ni-Si-Co-based copper alloy for electronic materials and method for producing the same
JP4620173B1 (en) Cu-Co-Si alloy material
JP4799701B1 (en) Cu-Co-Si based copper alloy strip for electronic materials and method for producing the same
WO2009122869A1 (en) Cu-Ni-Si-Co COPPER ALLOY FOR ELECTRONIC MATERIAL AND PROCESS FOR PRODUCING THE SAME
JP5451674B2 (en) Cu-Si-Co based copper alloy for electronic materials and method for producing the same
WO2012169405A1 (en) Copper alloy for electronic devices, method for producing copper alloy for electronic devices, copper alloy plastic working material for electronic devices, and component for electronic devices
KR101917416B1 (en) Copper-cobalt-silicon alloy for electrode material
JPWO2011036804A1 (en) Cu-Ni-Si-Co-based copper alloy for electronic materials and method for producing the same
WO2012043170A9 (en) Cu-Co-Si-BASED COPPER ALLOY FOR ELECTRONIC MATERIAL AND METHOD FOR PRODUCING SAME
JP6222885B2 (en) Cu-Ni-Si-Co based copper alloy for electronic materials
WO2012096351A1 (en) Cu-co-si-zr alloy material and method for producing same
JP5524901B2 (en) Cu-Ni-Si-Co based copper alloy for electronic materials
JP2012229467A (en) Cu-Ni-Si BASED COPPER ALLOY FOR ELECTRONIC MATERIAL
JP2012229469A (en) Cu-Si-Co BASED COPPER ALLOY FOR ELECTRONIC MATERIAL
JP5623960B2 (en) Cu-Ni-Si based copper alloy strip for electronic materials and method for producing the same
JP2016183418A (en) Cu-Ni-Si-Co-BASED COPPER ALLOY FOR ELECTRONIC MATERIAL
JP2013147687A (en) Titanium copper excellent in bendability
JP2012211350A (en) Cu-Ni-Si BASED COPPER ALLOY FOR ELECTRONIC MATERIAL AND METHOD OF MANUFACTURING THE SAME

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12734565

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 13979103

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2012734565

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20137021206

Country of ref document: KR

Kind code of ref document: A